CN101785087A

CN101785087A - Solution for removal of residue after semiconductor dry processing, and residue removal method using the same

Info

Publication number: CN101785087A
Application number: CN200880103849A
Authority: CN
Inventors: 中村新吾; 毛塚健彦
Original assignee: Daikin Industries Ltd
Current assignee: Daikin Industries Ltd
Priority date: 2007-08-22
Filing date: 2008-08-21
Publication date: 2010-07-21
Also published as: CN105543023A; KR20120115430A; KR101382998B1; TWI431113B; KR101382935B1; CN102839062A; JP4918939B2; KR20140018989A; KR20120115431A; KR101382700B1; US8822396B2; KR20100051717A; JPWO2009025317A1; TW200932899A; WO2009025317A1; US20100203735A1

Abstract

Disclosed is a solution for removing a residue after a dry processing, which can prevent the cracking or roughening of a Cu surface which cannot be overcome by a conventional liquid polymer stripper, which can prevent the oxidation of a Cu surface, and which contains a surface-protecting agent. Also disclosed is a method for producing a semiconductor device by using the solution. Specifically disclosed is a solution for removing a residue remaining on a semiconductor substrate after dry etching and/or ashing, which comprises: a Cu surface-protecting agent comprising at least one compound selected from the group consisting of (1) a compound which has, as a basic skeleton, a 5-membered heterocyclic aromatic compound having a structure represented by the formula: =N-NH- (provided that one having three contiguous N atoms is excluded) and which shows a pH value of 7 or less in the form of an aqueous solution (10 ppm, 23 DEG C); (2) a compound which has, as a basic skeleton, a 5-membered heterocyclic compound having a structure represented by the formula: -N=C(SH)-X- [wherein X represents NH, O or S] and which shows a pH value of 7 or less in the form of an aqueous solution (10 ppm, 23 DEG C) and (3) a compound which has, as a basic skeleton, a 6-membered heterocyclic aromatic compound having at least one nitrogen atom (N) and which shows a pH value of 7 or more in the form of an aqueous solution (10 ppm, 23 DEG C); a compound capable of forming a complex or chelate in coordination with Cu (copper); and water. The solution has a pH value ranging from 4 to 9.

Description

Residue after the semiconductor dry process is removed liquid and is used this residue to remove the residue removal method of liquid

Technical field

The present invention relates to be used for to remove the soup of the residue that when the dry ecthing of the manufacturing process of semiconductor equipment and/or ashing (ashing), forms and use this soup to remove the manufacture method of the semiconductor equipment of these residues.Be particularly related to the residue that in the manufacturing of Cu/Low-k multi-layer wiring structure, uses and remove liquid.

Background technology

All the time, use Al or Al alloy etc., use SiO as wiring material as interlayer dielectric ₂The Al/SiO of film ₂The semiconductor equipment of multi-layer wiring structure is made as core.In recent years, the distribution that causes postpones (interconnect delay) in order to reduce the miniaturization of following semiconductor equipment, makes the semiconductor equipment of the Cu/Low-k multi-layer wiring structure of the little interlayer dielectric Low-k film (film having low dielectric constant) of low wiring material Cu (copper) of use resistance and wiring closet capacity mostly.

In the Cu/Low-k multi-layer wiring structure, adopt the method that is called embedding (damascene, Damascus) to process.Embedding in (dualdamascene) as the two of a kind of method that embeds, at first on the interlayer dielectric substrate that constitutes by Low-k film etc., be formed for the ditch (trench) and the via (via hole) of distribution continuously by dry process.

Boring technology (via-first process) is one of method that is used to form two embedded structures earlier.In this technology,, after forming via on the interlayer dielectric substrate, will imbed agent and imbed also planarization by dry ecthing, be used to form the lithography of ditch at this, and carry out dry ecthing.Afterwards, remove unwanted resist and imbed agent from the interlayer dielectric substrate that is formed with groove (ditch) and hole (via) by ashing etc.

But,, the refuse (following these are called " residue after the dry process ") that can not remove fully arranged still residual on the substrate even through this technology.

In the ditch and via of embedded structure, if the residue have dry process when imbedding the metal of barrier metal TaN or wiring material Cu etc. after just becomes the bad reason of semiconductor equipment.Therefore, use residue such as polymer stripper to remove liquid and remove these residues.

Behind residue after removing dry process and the Cu oxide-film, in groove (ditch) and cave (via), imbed the wiring material of Cu etc., remove unwanted Cu part, make its planarization, form distribution structure by cmp (CMP).At this moment, the particle of metal and use in grinding etc. and metal ion etc. remain on the substrate surface.For they being removed the detergent remover behind the use cmp (CMP).

Cu surface after the dry process when forming embedding or two embedded structure sustains damage, and is poorer than originally on the structure.Therefore, remove processing,,, occur coarse sometimes on the Cu surface or produce be full of cracks along the crystal boundary on Cu surface if examine even under the situation of the corrosion that does not observe Cu integral body by the residue that utilizes polymer stripper etc. to carry out.The variation on small like this Cu surface impacts equipment performance probably.

Be easy to generate be full of cracks in particular cases, using anticracking additive, but may not give full play to its effect sometimes.And, in having the sulfur-containing compound of anti-crazing effect, have if a large amount of interpolation can make the composition of Cu variable color, in appearance can not be satisfactory.In addition, except be full of cracks, produce fine Cu rough surface sometimes.

And the Cu surface that sustains damage in dry process is oxidized easily, and after soups such as polymer stripper were handled, by moving between the technology etc., wafer was exposed in the atmosphere, therefore generates oxide-film on the surface of Cu metal wiring easily.This Cu oxide-film also becomes the bad reason of semiconductor equipment, causes the bad of goods easily.The Cu oxide-film can be by utilizing argon sputter or hydrogen reduction etc. remove, but utilize the sputter of argon easily damage to be caused on the Cu surface, if carry out hydrogen reduction, may produce be full of cracks along the crystal boundary on Cu surface.Therefore, prevent that the growth of Cu oxide-film is most important.

For example, in patent documentation 1, disclose following technology, in the clean treatment process behind cmp (CMP), utilized carboxylic acids detergent remover such as oxalic acid to carry out the processing of removing of metal pollutant, and simultaneously or use the anticorrisive agent of BTA etc. thereafter.

But BTA exists as a little less than the effect of the antioxidant of Cu and poor, big to the environmental impact problem of decomposability.In addition, in patent documentation 1, as the anticorrisive agent illustration indazole, but concrete soup and treatment conditions are not disclosed.And indazole is enumerated as an example of four member ring heterocyclic compound, and the record of apparent error is arranged technically.

And in 0032 section of patent documentation 1, having put down in writing and having used concentration of oxalic acid is 0.01～1% the aqueous solution (detergent remover).But under this concentration, the pH of oxalic acid aqueous solution is 1.5～3, because this pH is lower than the pKa=pH (=3.82) of oxalic acid, so have the weak effect prevent the Cu oxidation, be easy to generate Cu surface checking and coarse problem.

Therefore, wish that the residue develop after can preventing the oxidation on Cu surface certainly and having the dry process that prevents Cu surface checking and coarse function removes liquid, but at present still untappedly go out such product.

Patent documentation 1: TOHKEMY 2001-148385 communique

Summary of the invention

The object of the present invention is to provide a kind of residue after formula technology to remove liquid, its can realize using the indeterminable Cu of the preventing surface checking of existing polymer stripper and coarse, prevent the Cu surface oxidation simultaneously.Another object of the present invention is to provide a kind of manufacture method of using this residue to remove the semiconductor equipment of liquid.

In order to achieve the above object; the inventor furthers investigate; found that: comprise the Cu surface protectant that constitutes by compound group, the compound and the water that can form complex or chelate with Cu with regulation structure and characteristic; and pH is that 4～9 soup (residue remove liquid) can prevent Cu surface checking and coarse, and can prevent the oxidation on Cu surface.The inventor further studies, thereby has finished the present invention.

That is, the invention provides removing liquid and using this residue to remove the manufacture method of the semiconductor equipment of liquid of residue on a kind of following semiconductor substrate that is present in after dry ecthing and/or the ashing.

1. 1 kinds of residues of item are removed liquid; it is used to remove the residue on the semiconductor substrate that is present in after dry ecthing and/or the ashing, and it contains the Cu surface protectant, can form the compound and the water of complex or chelate with Cu (copper), and the pH that this residue is removed liquid is 4～9; wherein

At least a compound in Cu surface protectant following by being selected from (1), (2), (3) constitutes,

(1) be to contain to have formula: the five-ring heterocycles aromatic compound of structure shown in the=N-NH-(not comprising 3 compounds that N is continuous) is as the compound of basic framework, and the pH of its aqueous solution (10ppm, 23 ℃) is below 7,

(2) be to contain to have formula: the five member ring heterocyclic compound of structure shown in the-N=C (SH)-X-(in the formula, X represents NH, O or S) is as the compound of basic framework, and the pH of its aqueous solution (10ppm, 23 ℃) is below 7,

(3) be to contain hexa-member heterocycle aromatic compound with at least 1 nitrogen-atoms (N) compound as basic framework, the pH of its aqueous solution (10ppm, 23 ℃) is more than 7.

An item 2. as 1 a described residue are removed liquid, compound shown in above-mentioned (1) is to be selected from indazole class, pyrazoles and 1,2, the compound of 4-triazole type, compound shown in above-mentioned (2) is the compound of selected from mercapto imidazoles, Qiu Ji oxazole class, thyroidan class, mercaptothiazoline class, mercaptobenzimidazole class, mercaptobenzoxazole class and mercaptobenzothiazoler class, and the compound shown in above-mentioned (3) is the compound that is selected from pyridines, miazines, pyridazine class, pyrazine class, quinolines or quinazoline ditosylate salt, quinoxaline and cinnolines class.

Item 3. as item 1 or 2 a described residue are removed liquid, compound shown in above-mentioned (1) is to be selected from indazole, the 3-hydroxy indazole, 3-chloro-1H-indazole, the 5-Aminoindazole, the 6-Aminoindazole, the 5-nitro indazole, the 6-nitro indazole, 3-bromo-7-nitro indazole, the 7-nitro indazole, indazole-3-carboxylic acid, 1-benzyl-1H-indazole-3-alcohol, pyrazoles, 3,5-dimethyl pyrazole and 1,2, the compound of 4-triazole, compound shown in above-mentioned (2) is to be selected from 2-mercaptobenzimidazole, the 2-mercaptoimidazole, 2-Qiu Ji oxazole, the 2-mercaptobenzoxazole, the 2-thyroidan, the compound of 2-mercaptobenzothiazole and 2-thiazoline-2-mercaptan, compound shown in above-mentioned (3) is to be selected from picoline, aminopyridine, 2, the 4-di-amino-pyrimidine, 2,4, the 6-Triaminopyrimidine, pyridazine, the compound of the amino pyrazine of 3--2-carboxylic acid and 4-aminoquinoline.

An item 4. as 1,2 or 3 a described residue are removed liquid, and the compound more than 2 kinds in the described Cu surface protectant above-mentioned by being selected from (1)～(3) constitutes.

Each described residue is removed liquid in item 5. as the item 1～4, and the content that described residue is removed the Cu surface protectant in the liquid is 0.1～4000ppm.

Each described residue is removed liquid in item 6. as the item 1～5; the content that described residue is removed the Cu surface protectant that is made of the compound shown in above-mentioned (1) in the liquid is 0.1～3000ppm; the content of the Cu surface protectant that is made of the compound shown in above-mentioned (2) is 0.1～5ppm, and the content of the Cu surface protectant that is made of the compound shown in above-mentioned (3) is 10～1000ppm.

Each described residue is removed liquid in 7. as 1～6, the described compound that can form complex or chelate with Cu be ketone acid, ketone acid salt, aldehydic acid salt, multi-carboxylate, can with Cu form complex or chelate strong acid, having can be at the neutral organic solvent of the oxygen atom of coordination on the Cu and/or the monohydric alcohol more than the C4.

8. as 7 a described residue remove liquid, the described compound that can form complex or chelate with Cu is at least a kind that is selected from ketone acid, ketone acid salt and the aldehydic acid salt.

9. as 7 a described residue remove liquid, the described compound that can form complex or chelate with Cu is the strong acid and the multi-carboxylate that can form complex or chelate with Cu.

10. as 7 a described residue remove liquid, the described compound that can form complex or chelate with Cu is that have more than 2 can be at the neutral organic compound of the oxygen atom of coordination on the Cu and/or the monohydric alcohol more than the C4.

11. as 7 a described residue remove liquid, the described compound that can form complex or chelate with Cu is a perchlorate.

Each described residue is removed liquid in item 12. as the item 1～11, also contains fluorine compounds.

Each described residue is removed liquid in item 13. as the item 1～12, also contains surfactant.

The method of removing of 14. 1 kinds of residues, the residue that it is used to remove on the semiconductor substrate that is present in after dry ecthing and/or the ashing makes in semiconductor substrate and the item 1～13 after dry ecthing and/or the ashing each described residue remove liquid and contacts.

15. as 14 a described residue removal method, described semiconductor substrate have Cu as wiring material, have film having low dielectric constant (Low-k film) as interlayer dielectic.

The manufacture method of 16. 1 kinds of semiconductor equipments, it comprises: (1) to have Cu as wiring material, have film having low dielectric constant (Low-k film) carries out dry ecthing and/or ashing as the semiconductor substrate of interlayer dielectic operation; (2) make in semiconductor substrate and the item 1～13 after handling by above-mentioned (1) each described residue remove the operation that liquid contacts.

The manufacture methods of an item 17. as 16 a described semiconductor equipment comprise that also (3) will be heated to the operation more than 180 ℃ by the semiconductor substrate after above-mentioned (2) processing in inert gas or in the vacuum.

The invention effect

Remove liquid if use the residue after the dry process of the present invention, can remove the residue that is present on the semiconductor substrate, and can realize using the indeterminable damage that prevents to be subjected to dry process of existing polymer stripper and the small be full of cracks and the rough surface on incidental Cu surface, and also can prevent because the damage of dry process and the oxidation on the Cu surface of oxidation easily.

All the time, for the be full of cracks that prevents the Cu surface fully, coarse and oxidation, the soup composition is limited sometimes, but remove in the liquid at residue of the present invention, because can select soup composition widely, thus soup can be adopted with variation, and help the minimizing of manufacturing cost.

In addition, because the variable color etc. of the Cu that causes owing to the Cu surface protectant that adds can not take place, so also there is not apparent problem, this Cu surface protectant decomposes easily, so also little to the influence of environment.

Thus, because residue of the present invention is removed the Cu surface protectant that liquid contains regulation, so can help to produce bad few semiconductor equipment.

Embodiment

Below describe the present invention in detail.

I. the residue after the semiconductor dry process is removed liquid

Residue of the present invention is removed liquid and is used to remove residue on the semiconductor substrate that is present in after dry ecthing and/or the ashing; it is characterized in that: contain the Cu surface protectant, can form the compound and the water of complex or chelate with Cu; the pH that this residue is removed liquid is 4～9; wherein; at least a compound in Cu surface protectant following by being selected from (1), (2), (3) constitutes

The pH that residue after the dry process of the Cu of containing surface protectant of the present invention is removed liquid is 4～9, is preferably 4～8, more preferably 5～7.If, preventing Cu surface checking, effect coarse and oxidation less than 4, will weaken pH; PH is 4 when above, and its effect is strong.In addition, use at dielectric film under the situation of porous Low-k, less than 4 o'clock surface modification might take place, so preferred pH is more than 4 at pH.If pH is greater than 9, though have the effect of Cu surface protectant, the natural oxide film of Cu and the residue after the dry process are removed effect and are weakened, and the Low-k film is caused the surface modification equivalent damage.

Further as required, add fluorine compounds, perchlorate, surfactant etc., can increase more excellent function.

The Cu surface protectant

At least a compound that residue of the present invention is removed in the Cu surface protectant that uses in the liquid following by being selected from (1), (2), (3) constitutes,

(1) be to contain to have formula: the five-ring heterocycles aromatic compound of structure shown in the=N-NH-(not comprising 3 compounds that N is continuous) is as the compound of basic framework, and the pH of its aqueous solution (concentration 10ppm, 23 ℃) is below 7,

(2) be to contain to have formula: the five member ring heterocyclic compound of structure shown in the-N=C (SH)-X-(in the formula, X represents NH, O or S) is as the compound of basic framework, and the pH of its aqueous solution (concentration 10ppm, 23 ℃) is below 7,

In any compound of above-mentioned (1)～(2), the pH of its aqueous solution (concentration 10ppm, 23 ℃) is that the proton of expression below 7 is in and is difficult to the state that combines with the unshared electron pair of nitrogen-atoms in the molecule, and preferred pH is 3～7, and more preferably pH is 4～6.5.In the compound of above-mentioned (3), the pH of its aqueous solution (10ppm, 23 ℃) is that the expression proton is in easily the state that combines with the unshared electron pair of nitrogen-atoms in the molecule more than 7, and preferably pH is 7～11, and more preferably pH is 8～10.

Compound shown in above-mentioned (1) can contain and has formula: the five-ring heterocycles aromatic compound of structure shown in the=N-NH-(not comprising 3 compounds that N is continuous) is as basic framework, also can be the compound that this basic framework and other aromatic rings (for example phenyl ring etc.) ring contracts and obtains.Be defined as so-called π-superfluous N-heteroaromatic compound.This compound also can have substituting group on its ring, for example, can have the substituting group of 1～3 alkyl (preferred C1-3 alkyl), hydroxyl, amino, nitro, halogen atom (for example fluorine atom, chlorine atom, bromine atoms etc.), carboxyl etc.

As the object lesson of the compound shown in above-mentioned (1), can enumerate indazole class, pyrazoles and 1,2,4-triazole type etc.More specifically, as the indazole class, for example can enumerate indazole, 3-hydroxy indazole, 3-chloro-1H-indazole, 5-Aminoindazole, 6-Aminoindazole, 5-nitro indazole, 6-nitro indazole, 3-bromo-7-nitro indazole, 7-nitro indazole, indazole-3-carboxylic acid, 1-benzyl-1H-indazole-3-alcohol.As pyrazoles, can enumerate pyrazoles, 3,5-dimethyl pyrazole etc.As 1,2, the 4-triazole type for example can enumerate 1,2,4-triazole etc.Wherein, preferred indazole, 3-chloro-1H-indazole, indazole-3-carboxylic acid and 5-nitro indazole.Indazole, 5-nitro indazole and indazole-3-carboxylic acid most preferably.

The Cu surface protectant that is made of the compound shown in above-mentioned (1) has the feature of the excellence of the oxidation that can prevent the Cu surface and be full of cracks and coarse all situations.Therefore, be suitable as residue most and remove Cu surface protectant contained in the liquid.

Compound shown in above-mentioned (2) can contain and has formula :-N=C (SH)-X-is (in the formula, X represents NH, O or S) shown in the five member ring heterocyclic compound of structure as basic framework, also can be the compound that this basic framework and other aromatic rings (for example phenyl ring etc.) ring contracts and obtains.Be defined as so-called π-superfluous N-, O-or S-heteroaromatic compound.This compound also can have substituting group on its ring, for example, can have the substituting group of 1～3 alkyl (preferred C1-3 alkyl), hydroxyl, amino, nitro, halogen atom (for example fluorine atom, chlorine atom, bromine atoms etc.), carboxyl etc.

As the object lesson of the compound shown in above-mentioned (2), can enumerate mercaptoimidazole class, Qiu Ji oxazole class, thyroidan class, mercaptothiazoline class, mercaptobenzimidazole class, mercaptobenzoxazole class or mercaptobenzothiazoler class etc.More specifically, can enumerate 2-mercaptobenzimidazole, 2-mercaptoimidazole, 2-Qiu Ji oxazole, 2-mercaptobenzoxazole, 2-thyroidan, 2-mercaptobenzothiazole, 2-thiazoline-2-mercaptan etc.Wherein, preferred 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-thiazoline-2-mercaptan.Most preferably 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-thiazoline-2-mercaptan.

By the Cu surface protectant that the compound shown in above-mentioned (2) constitutes, mainly has the feature that can prevent Cu surface oxidation and coarse excellence.

With the compound shown in above-mentioned (3) can contain have at least 1 nitrogen-atoms (N) the hexa-member heterocycle aromatic compound as basic framework, also can be the compound that this basic framework and other aromatic rings (for example phenyl ring etc.) ring contracts and obtains.Be defined as so-called π-shortcoming N-heteroaromatic compound.This compound also can have substituting group on its ring, for example, can have the substituting group of 1～3 alkyl (preferred C1-3 alkyl), hydroxyl, amino, nitro, halogen atom (for example fluorine atom, chlorine atom, bromine atoms etc.), carboxyl etc.

As the object lesson of the compound shown in above-mentioned (3), for example, can enumerate pyridines, miazines, pyridazine class, pyrazine class, quinolines, quinazoline ditosylate salt, quinoxaline, cinnolines class etc.More specifically, can enumerate picoline, aminopyridine, 2,4-di-amino-pyrimidine, 2,4,6-Triaminopyrimidine, pyridazine, the amino pyrazine of 3--2-carboxylic acid, 4-aminoquinoline etc.Wherein, preferred 2,4-di-amino-pyrimidine, 2,4,6-Triaminopyrimidine.Most preferably 2,4, the 6-Triaminopyrimidine.

The Cu surface protectant that is made of the compound shown in above-mentioned (3) mainly has the feature that can prevent the shaggy excellence of Cu.

Can think the Cu surface be full of cracks, coarsely cause by different reasons respectively, so not necessarily must use a kind of Cu surface protectant to prevent these situations with oxidation.In addition, in order to replenish the effect that prevents these situations, preferably, from above-claimed cpd, mix more than 2 kinds and use according to the situation on Cu surface.

Owing to cost an arm and a leg and if excessively interpolation can cause removing property of residue decline after the dry process, so in the concentration range that continues the performance effect, the addition of Cu surface protectant is few more good more.In order to continue the performance effect, residue remove in the liquid can be for 0.1～4000ppm about, be preferably about 0.25～2000ppm.

The concentration of the Cu surface protectant that is made of the compound shown in above-mentioned (1) is generally about 0.1～3000ppm; but when residue is removed the material that does not contain carboxyl in the liquid; perhaps to remove the pH of liquid be that the pH of pKa=pH of carboxylic material is when above containing carboxylic material, this residue; be generally 0.1ppm～100ppm; be preferably 0.1ppm～10ppm, more preferably 0.1ppm～1ppm.

Containing pH that carboxylic material, this residue remove liquid for the time less than the pH of the pKa=pH of carboxylic material, be 1ppm～3000ppm, be preferably 5ppm～2000ppm, more preferably 100ppm～1000ppm.

Compound shown in above-mentioned (1) is a slightly soluble in water usually, and from the relation of solubility, its working concentration is restricted mostly.In addition, if a large amount of the interpolation makes removing property of the residue decline after the dry process sometimes.For the solubility that makes the Cu surface protectant increases, and prevent from preferably as required, to remove the organic solvent that adds in the liquid more than the 10 weight %, about preferred 10～50 weight % at residue owing to adding the decline that the Cu surface protectant causes removing property of residue.Containing pH that carboxylic material, this residue remove liquid for the time, under the concentration of Cu surface protectant is situation more than the 100ppm, containing organic solvent usually less than the pH of the pKa=pH of carboxylic material.

The concentration of the Cu surface protectant that is made of the compound shown in above-mentioned (2) is 0.1ppm～50ppm, is preferably 0.1ppm～5ppm, more preferably 0.1ppm～1ppm.

The concentration of the Cu surface protectant that is made of the compound shown in above-mentioned (3) is 10ppm～1000ppm, is preferably 50ppm～500ppm, more preferably 100ppm～300ppm.

When being the mixed system of the compound shown in above-mentioned (1)～(3), the preferred content more than at least 2 kinds (concentration) wherein is 0.2ppm～3000ppm.

Can form the compound of complex or chelate with Cu

As long as removing the composition of liquid, the residue after the dry process of interpolation Cu surface protectant can remove the residue that contains Cu, Si, organic substance etc.; be not particularly limited; but, must contain the compound that can form complex or chelate with Cu in order to remove Cu residue as main component.

As the compound that can form complex or chelate with Cu, for example, can enumerate ketone acid, ketone acid salt, aldehydic acid salt, multi-carboxylate, can with Cu form complex or chelate strong acid, having can be at the neutral organic solvent of the oxygen atom of coordination on the Cu, the monohydric alcohol more than the C4 etc.Be adjusted to 4～9 as long as residue can be removed the pH of liquid, can be from these compounds combination in any.

As ketone acid, for example, can enumerate pyruvic acid, levulic acid, 5-amino-laevulic acid, KG, acetone dicarboxylic acid etc.

As ketone acid salt, for example, can enumerate the salt that the alkali by the ketone acid of above-mentioned pyruvic acid, levulic acid, 5-amino-laevulic acid, KG, acetone dicarboxylic acid etc. and ammonia, azanol, primary amine, secondary amine or tertiary amine, quaternary ammonium, polyamine etc. forms.Wherein, be preferably selected from the salt that pyruvic acid and levulic acid and ammonia, methylamine, ethamine, propylamine, butylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, propane diamine, trien, Tetramethylammonium hydroxide and choline (choline) form at least a kind.More preferably the diethyl amine salt of pyruvic acid, Tetramethylammonium hydroxide salt or choline salt, the perhaps methylamine salt of levulic acid, ethylamine salt, diethyl amine salt.

As aldehydic acid salt, for example, can enumerate at least a kind in the salt that alkali such as being selected from glyoxalic acid and ammonia, azanol, primary amine, secondary amine or tertiary amine, quaternary ammonium, polyamine forms.Wherein, butylamine salt, diethyl amine salt, Tetramethylammonium hydroxide salt or the choline salt of preferred glyoxalic acid.

The salt of ketone acid or the salt of aldehydic acid can use with the form of crystallization, also can use the aqueous solution that mixes these bronsted lowry acids and bases bronsted lowry neutralizations and generate in water.

Residue is removed at least a kind the concentration in ketone acid, ketone acid salt and the aldehydic acid salt of being selected from the liquid, can suitably select according to the amount and the matter of the residue after the dry process of removing.

Remove in the liquid at residue, be selected from least a kind the use level (concentration) in ketone acid, ketone acid salt and the aldehydic acid salt, usually can be for about 0.1～35 weight %.

Particularly, remove in the liquid at residue, it is just enough that the use level of ketone acid (concentration) is generally 0.5～10 weight %, is preferably 1～5 weight %, more preferably 1～3 weight %.Their concentration is low more, and it is just weak more that residue is removed effect; Concentration is high more, removes effect and prolongs with regard to the life-span high more, soup, but owing to be acid, so be easy to generate the viewpoint of be full of cracks and relative costs effect from the Cu surface, be preferably below the 10 weight %.

In addition, remove in the liquid at residue, it is just enough that the use level (concentration) of aldehydic acid salt and/or ketone acid salt is generally 0.1～35 weight %, is preferably 0.3～15 weight %, more preferably 0.5～10 weight %.Their concentration is low more, and it is just weak more that residue is removed effect, when being lower than 0.1 weight % especially a little less than.Concentration is high more, removes that effect is just high more, the life-span of soup prolongs, but from the viewpoint of relative costs effect, is preferably below the 35 weight %.

As the multi-carboxylate, for example, can enumerate in the salt that alkali such as polycarboxylic acids such as being selected from oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, malic acid, tartaric acid, diammonium hydrogen citrate, ammonium dihydrogen citrate, citric acid and ammonia, azanol, alkanolamine, primary amine, secondary amine or tertiary amine, quaternary ammonium, polyamine form at least a kind.Preferably enumerate the salt that alkali such as polycarboxylic acid such as oxalic acid, malonic acid, diammonium hydrogen citrate, ammonium dihydrogen citrate, citric acid and ammonia, primary amine, secondary amine or tertiary amine, quaternary ammonium, alkanolamine, polyamine form.

More specifically, can enumerate oxalic acid, malonic acid, diammonium hydrogen citrate, ammonium dihydrogen citrate, polycarboxylic ammonium salt such as citric acid, methylamine salt, ethylamine salt, propylamine salt, butylamine salt, dimethylamine salt, the diethyl amine salt, the front three amine salt, triethylamine salt, ethanolamine salt, diethanolamine salt, triethanolamine salt, the diisopropanol amine salt, triisopropanolamine salt, the isopropyl alcohol amine salt, the normal propyl alcohol amine salt, N, N-dimethyl ethanol amine salt, N-methyl ethanol amine salt, N methyldiethanol amine salt, N-acetyl ethanonlamine salt, N-ethyl hexanol amine salt, propane diamine salt, trien salt, Tetramethylammonium hydroxide salt, choline salt etc.

Wherein, the most preferably ammonium salt of oxalic acid, methylamine salt, the ammonium salt of malonic acid, methylamine salt, ethylamine salt, Tetramethylammonium hydroxide salt or choline salt; The methylamine salt of diammonium hydrogen citrate, ethylamine salt, Tetramethylammonium hydroxide salt or choline salt; The methylamine salt of ammonium dihydrogen citrate, ethylamine salt, Tetramethylammonium hydroxide salt or choline salt; Ammonium salt, methylamine salt, ethylamine salt, Tetramethylammonium hydroxide salt or choline salt with citric acid.

The multi-carboxylate can use with the form of crystallization, also can use the aqueous solution that mixes these bronsted lowry acids and bases bronsted lowry neutralizations and generate in water.Remove in the liquid at residue, multi-carboxylate's use level (concentration) is 0.1～20 weight %, is preferably 0.5～10 weight %, more preferably 1～5 weight %.

As neutral organic compound with oxygen atom that can coordination on Cu, can be the organic compound that Cu is had the neutrality of oxygen coordination site, so-called neutral, the expression proton is supplied with property solvent (acidity) and protophilia solvent (alkalescence) character in addition.For example, can enumerate poly-carbonyl class (polycarbonyls), ketols, hydroxy ester class, diester class, keto ester class, lactone, carbonates, polyethers, glycols, alkylene glycol mono ethers, aklylene glycol diester class, aklylene glycol ether-ether class, polyalkylene glycols, polyalkylene glycol mono ethers, PAG diester class, polyalkylene glycol ethers ester class etc.

As poly-carbonyl class, for example, can enumerate twain-aldehyde compound (for example glyoxal etc.), two ketones (2,3-diacetyl, 2,4-pentanedione (acetylacetone,2,4-pentanedione, 2,3-pentanedione, 1,2-cyclohexanedione, 3,4-acetyl butyryl etc.), keto-aldehyde class (methyl-glyoxal etc.).Wherein, preferred 2, the 3-diacetyl.

As the ketone acid alcohols, for example, can enumerate 3-hydroxy-2-butanone (acetoin), diacetone alcohol, pyruvic alcohol etc.Wherein preferred 3-hydroxy-2-butanone.

As the hydroxy ester class, for example, can enumerate methyl lactate, ethyl lactate, butyl lactate, methyl glycollate, ethyl glycolate, dimethyl tartrate, ethyl tartrate, methyl glycollate etc.Wherein, preferred ethyl lactate, methyl glycollate.

As the diester class, for example, can enumerate dimethyl oxalate, diethy-aceto oxalate, dimethyl malenate, diethyl malonate, dimethyl succinate, diethyl succinate, dimethyl glutarate, ethyl glutarate, dimethyl adipate, dimethyl maleate etc.Wherein, preferred dimethyl oxalate, diethy-aceto oxalate, dimethyl malenate, diethyl malonate.

As the keto ester class, for example, can enumerate methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, oxopentanoic acid butyl ester etc.Wherein, preferred methyl acetoacetate, ethyl acetoacetate.

As lactone, for example, can enumerate gamma-butyrolacton, glucopyrone, δ-Wu Neizhi etc.Wherein, preferred gamma-butyrolacton.

As carbonates, for example, can enumerate propene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate etc.Wherein, preferred propene carbonate.

As polyethers, for example, can enumerate glycol dialkyl ether (dimethoxymethane, dimethoxy-ethane, diethoxymethane, the Ethylene Glycol Methyl ethylether, dimethoxy-ethane, diethoxymethane, diethoxyethane, the ethylene glycol bisthioglycolate n-butyl ether, dimethoxy propane etc.), PAG dialkyl ether (diethylene glycol dimethyl ether, the diethylene glycol (DEG) methyl ethyl ether, diethyl carbitol, the diethylene glycol (DEG) di-n-butyl ether, triglyme, triethylene glycol ethyl-methyl ether, the triethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, the tetraethylene glycol diethyl ether, Polyethylene glycol dimethyl ether etc.) etc.Wherein, preferred dimethoxy-ethane, diethylene glycol dimethyl ether, diethyl carbitol, triglyme, tetraethylene glycol dimethyl ether.

As glycols, for example, can enumerate ethylene glycol, 1, ammediol, 1,2-propylene glycol, glycerol, 1,2-cyclohexanediol, 2,2-dimethyl-1, ammediol, 2,5-dimethyl-2,5-hexylene glycol, 2,3-naphthalene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2-butine-1,4-glycol, 2-butene-1,4-glycol, DL-1,2-hexylene glycol, 2,5-hexylene glycol, 1,2-Benzenediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol etc.Wherein, preferred ethylene glycol, 1, ammediol, 1,2-propylene glycol.

As the alkylene glycol mono ethers, for example, can enumerate glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, glycol monomethyl phenyl ether etc.Wherein, preferred glycol monoethyl ether, ethylene glycol monoethyl ether.

As aklylene glycol diester class, for example, can enumerate ethylene acetate, propylene-glycol diacetate etc.Wherein, preferred ethylene acetate.

As aklylene glycol ether-ether class, for example, can enumerate ethylene glycol monomethyl ether acetate, ethylene glycol monoethylether acetate, propylene glycol methyl ether acetate, ethylene glycol mono-n-butyl ether acetic acid esters, propylene glycol-1-methyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetic acid esters etc.Wherein, preferred ethylene glycol monomethyl ether acetate, ethylene glycol monoethylether acetate.

As polyalkylene glycols, for example, can enumerate diethylene glycol (DEG), triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, poly-(propylene glycol), glycerol etc.Wherein, preferred diethylene glycol (DEG), triethylene glycol.

As the polyalkylene glycol mono ethers, for example, can enumerate diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diglycol monotertiary isobutyl ether, diglycol monotertiary n-butyl ether, diglycol monotertiary benzyl oxide, diglycol monotertiary hexyl ether, diglycol monotertiary benzyl oxide, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol list dodecyl ether, heptandiol list dodecyl ether, poly glycol monomethyl ether etc.Wherein, alkoxyl alcohols such as preferred diethylene glycol monomethyl ether, diethylene glycol monoethyl ether.

As PAG diester class, for example, can enumerate diethylene glycol diacetate, triethylene-glycol diacetate etc.Wherein, preferred diethylene glycol diacetate.

As polyalkylene glycol ethers ester class, for example, can enumerate diethylene glycol monomethyl ether acetic acid esters, diethylene glycol monoethyl ether acetic acid esters, diglycol monotertiary n-butyl ether acetic acid esters, triethylene glycol monomethyl ether acetic acid esters, triethylene glycol monoethyl ether acetate etc.Wherein, preferred diethylene glycol monomethyl ether acetic acid esters.

In above-mentioned neutral organic compound, preferably enumerate 2, the 3-diacetyl, 3-hydroxy-2-butanone, ethyl lactate, methyl glycollate, dimethyl oxalate, diethy-aceto oxalate, dimethyl malenate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, gamma-butyrolacton, propene carbonate, dimethoxy-ethane, diethylene glycol dimethyl ether, diethyl carbitol, triglyme, tetraethylene glycol dimethyl ether, ethylene glycol, 1, ammediol, 1, the 2-propylene glycol, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethylether acetate, diethylene glycol (DEG), triethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diacetate, diethylene glycol monomethyl ether acetic acid esters etc.

In addition, in above-mentioned neutral organic compound, as other preferred compound, from can not causing the aspect of damaging and more effectively suppressing the be full of cracks on Cu surface, can enumerate ketols, hydroxy ester class, diester class, keto ester class, lactone, carbonates, aklylene glycol diester class, aklylene glycol ether-ether class, PAG diester class, polyalkylene glycol ethers ester class etc. to the Low-k film.

Particularly, can enumerate ethyl lactate, methyl glycollate, dimethyl oxalate, diethy-aceto oxalate, dimethyl malenate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, gamma-butyrolacton, propene carbonate, ethylene acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethylether acetate, diethylene glycol diacetate, diethylene glycol monomethyl ether acetic acid esters etc.

In addition, as the monohydric alcohol more than the C4, for example, can enumerate the monohydric alcohol of C4～7 such as 1-butanols, the tert-butyl alcohol, isobutanol, sec-butyl alcohol, amylalcohol, hexanol, enanthol.Wherein, preferred 1-butanols, isobutanol, sec-butyl alcohol.

Remove in the liquid at residue, the use level (concentration) of the ethanol that neutral organic compound and/or C4 are above is 0.1～60 weight %, is preferably 1～40 weight %, more preferably 2～15 weight %.

In the above-mentioned neutral organic compound, also have and have the compound that in the aqueous solution, is subjected to the ester group of hydrolysis easily.For example, can enumerate hydroxy ester class, diester class, keto ester class, lactone, carbonates, aklylene glycol diester class, aklylene glycol ether-ether class, PAG diester class and polyalkylene glycol ethers ester class.For such ester class, more preferably remove in the liquid to add and be used for neutralizing hydrolysis and generate H at residue ⁺Water-soluble alkali or be used to control the H of generation ⁺The multi-carboxylate.Contain Cu by adding the multi-carboxylate, increasing _xThe antiseptic effect of removing effect and Cu of O residue.When using amine and when adding polycarboxylic amine salt, prevent that the effect of Cu surface checking also is enhanced as water-soluble alkali, thus preferred.

As water miscible alkali, for example, can enumerate ammonia, azanol, primary amine, secondary amine or tertiary amine (methylamine, ethamine, propylamine, butylamine, dimethylamine, diethylamine, di-n-propylamine, trimethylamine, triethylamine etc.), quaternary ammonium (Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, choline etc.), polyamine (hydrazine, ethylenediamine, propane diamine, diethylenetriamines, triamido triethylamine, trien etc.) etc.Wherein, preferred ethamine, diethylamine, Tetramethylammonium hydroxide, choline, propane diamine, trien etc.

The use level of water-soluble alkali is so long as be used for pH is neutralized 4～7 and the appropriate amount that adds gets final product.Therefore, also depend on the amount of ester amount and hydrolysis thereof, and hydrolysis also depends on temperature and other composition, so generally will not determine.The preferred appropriate amount that adds, the pH that neutralizes is 5～7, the pH that more preferably neutralizes is 6～7.

Can also add perchlorate.As perchlorate, be the salt that forms by at least a kind that is selected from ammonia, azanol, primary amine, secondary amine or tertiary amine, quaternary ammonium and the polyamine, can enumerate ammonium perchlorate, Thyronorman's amine salt, perchloric acid propane polyamine salt, perchloric acid trien salt etc.Wherein, preferred ammonium perchlorate.

Remove in the liquid at residue, the use level of perchlorate (concentration) is 0.1～10 weight %, is preferably 0.3～5 weight %, more preferably 0.5～3 weight %.

Can form the strong acid of complex or chelate with Cu, the pKa that is 25 ℃ is the Bronsted acid of (be preferably below 2, more preferably 0～2) below 3, supplies with hydrogen ion H ⁺With form the reagent (part) of chelate or complex with Cu, have the function of the residue after the dry process of removing.

As object lesson, can enumerate Halogen carboxylic acids such as chloroacetic acid, dichloroacetic acid, trichloroacetic acid, α-chloro-butyric acid, β-chloro-butyric acid, γ-chloro-butyric acid, a fluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, inorganic acids such as hydrobromic acid, perchloric acid, sulfuric acid, polycarboxylic acids such as oxalic acid, malonic acid, tartaric acid, citric acid etc.Wherein, preferred oxalic acid, malonic acid, citric acid, trifluoroacetic acid, hydrobromic acid, perchloric acid, more preferably oxalic acid, malonic acid, citric acid, trifluoroacetic acid.

This strong acid is removed concentration in the liquid at residue, can suitably select according to the amount and the matter of the residue after the dry process of removing.Remove in the liquid at residue, the use level of this strong acid (concentration) is generally about 0.1～10 weight %, is preferably 0.1～5 weight %, more preferably 0.1～3 weight %.Their concentration is low more, and the residue after the dry process is difficult more to be removed; Concentration is high more, and removing of residue is just easy more.From the viewpoint of relative costs effect, be preferably below the 5 weight %.

Can form the compound of complex or chelate with Cu from these and select arbitrarily, as exemplary, can the following form of illustration.

For example, can enumerate (A) be selected from that in ketone acid, ketone acid salt and the aldehydic acid salt at least a kind, (B) can have with combination, (C) that Cu forms the strong acid of complex or chelate and multi-carboxylate more than 2 can be at the neutral organic compound of the oxygen atom of coordination on the Cu and/or combination, (D) perchlorate of the monohydric alcohol more than the C4.And the object lesson that the residue that contains above-mentioned (A)～(D) is removed liquid is set forth in the back.

Even just contain the soup of above-mentioned (A)～(D), prevent that the be full of cracks on Cu surface, effect coarse and oxidation are also very high, but when further adding above-mentioned Cu surface protectant, this effect becomes higher.

Fluorine compounds

Further add fluorine compounds in the liquid by removing, can improve the effect of removing the residue that on the sidewall of the pattern that forms on the interlayer dielectrics such as Low-k film, adheres at residue of the present invention.This residue is except Cu sex change beyond the region of objective existence, barrier film and Low-k films such as SiN, imbed agent etc. in dry ecthing by sputter, contain Si and organic substance sometimes.When worrying whether this residue can fully be removed or can not remove,, can add the low amount of fluorinated compound in order to append the higher effect of removing.

As fluorine compounds, for example, can enumerate the fluoride salt of hydrogen fluoride or ammonia, azanol, primary amine, secondary amine or tertiary amine, quaternary ammonium or polyamine etc. etc.Particularly, preferred fluorinated hydrogen, ammonium fluoride, a hydrogen fluoram, fluoridize methylamine, fluoridize ethamine, fluoridize diethylamine, fluoridize trien, Methanaminium, N,N,N-trimethyl-, fluoride etc.It also can be more than 2 kinds that fluorine compounds can be a kind.As 1 execution mode of the present invention, for example, can use ammonium fluoride aqueous solution, diluted hydrofluoric acid (the 50 weight % aqueous solution).

The use level of fluorine compounds (concentration) can be according to containing interlayer dielectric such as silicon fiml, Low-k film and because dry process is subjected to the kind and the amount of the interlayer dielectric of plasma damage suitably selects.

Remove in the liquid at residue, the preferred use level of fluorine compounds (concentration) is 0.001～5 weight %, more preferably 0.01～3 weight %.The part that is subjected to plasma damage that suppresses interlayer dielectric at needs is by of the present invention when removing liquid corrosion and carving, preferably do not contain or on a small quantity (1 weight % is following) cooperate fluorine compounds.But if less than 0.001 weight %, the effect of removing residue will descend.

Surfactant

Remove in the liquid at residue of the present invention and can also add surfactant.Surfactant is used for hydrophobic interlayer dielectric is increased wetability, prevents soup because the shape of pattern and the situation that can not spread all over etc.Its kind can be cationic, anionic, nonionic etc., is not particularly limited.Concentration is 0.00001～5 weight %, is preferably 0.0001～3 weight %.If less than 0.00001 weight %, the surface activity effect is little; Even if greater than 5 weight %, its effect does not change yet.

Remove in the liquid at residue, the ratio that residue of the present invention is removed water contained in the liquid is generally about 40～99.5 weight %, is preferably about 50～99 weight %, can be according to the use level decision of the composition beyond the water.

Residue after the semiconductor dry process is removed the concrete example of liquid

Residue is removed liquid (A)

Residue of the present invention is removed liquid and is characterised in that, contains at least a kind of being selected from ketone acid, ketone acid salt and the aldehydic acid salt, Cu surface protectant and water as basic composition.By further interpolation multi-carboxylate, neutral organic compound, surfactant, fluorine compounds, antioxidant, anticracking additive etc., can increase more excellent function with oxygen atom that can coordination on Cu.

The kind of Cu surface protectant and use level thereof can be enumerated above-mentioned item.

Be selected from the function of the residue after in ketone acid, ketone acid salt and the aldehydic acid salt at least a kind has the burn into that suppresses Cu and removes dry process.The burn into that also has a Cu piece that not only can suppress common can also suppress the feature of the be full of cracks on small Cu surface.

As the salt of ketone acid, for example, can enumerate the salt that the alkali by the ketone acid of above-mentioned pyruvic acid, levulic acid, 5-amino-laevulic acid, KG, acetone dicarboxylic acid etc. and ammonia, azanol, primary amine, secondary amine or tertiary amine, quaternary ammonium, polyamine etc. forms.Wherein, be preferably selected from the salt of at least a formation at least a and ammonia, methylamine, ethamine, propylamine, butylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, propane diamine, trien, Tetramethylammonium hydroxide and the choline in pyruvic acid and the levulic acid.More preferably the diethyl amine salt of pyruvic acid, Tetramethylammonium hydroxide salt or choline salt, the perhaps methylamine salt of levulic acid, ethylamine salt or diethyl amine salt.

As the salt of aldehydic acid, for example, can enumerate the salt that alkali such as glyoxalic acid and ammonia, azanol, primary amine, secondary amine or tertiary amine, quaternary ammonium, polyamine form.Wherein, butylamine salt, diethyl amine salt, Tetramethylammonium hydroxide salt or the choline salt of preferred glyoxalic acid.

Remove in the liquid at residue, be selected from least a kind the use level (concentration) in ketone acid, ketone acid salt and the aldehydic acid salt, be generally about 0.1～35 weight %.

Add the multi-carboxylate in the liquid by further removing, the effect of the residue after can increasing the effect that prevents the Cu surface checking and removing dry process at residue.The effect that particularly polycarboxylic amine salt prevents the Cu surface checking is strong.As this multi-carboxylate, for example, can enumerate the salt that alkali such as polycarboxylic acid such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, malic acid, tartaric acid, diammonium hydrogen citrate, ammonium dihydrogen citrate, citric acid and ammonia, azanol, primary amine, secondary amine or tertiary amine, quaternary ammonium, alkanolamine, polyamine form.Preferably enumerate the salt that alkali such as polycarboxylic acid such as oxalic acid, malonic acid, diammonium hydrogen citrate, ammonium dihydrogen citrate, citric acid and ammonia, primary amine, secondary amine or tertiary amine, quaternary ammonium, alkanolamine, polyamine form.

Particularly, polycarboxylic ammonium salt, methylamine salt, ethylamine salt, diethyl amine salt, triethylamine salt, ethanolamine salt, diethanolamine salt, triethanolamine salt, diisopropanol amine salt, triisopropanolamine salt, isopropyl alcohol amine salt, normal propyl alcohol amine salt, N such as preferred oxalic acid, malonic acid, diammonium hydrogen citrate, ammonium dihydrogen citrate, citric acid, N-dimethyl ethanol amine salt, N-methyl ethanol amine salt, N methyldiethanol amine salt, N-acetyl ethanonlamine salt, N-ethyl hexanol amine salt, trien salt, Tetramethylammonium hydroxide salt and choline salt.

These multi-carboxylates can use with the form of crystallization, also can use the aqueous solution that mixes these bronsted lowry acids and bases bronsted lowry neutralizations and generate in water.Remove in the liquid at residue, multi-carboxylate's use level (concentration) is 0.1～15 weight %, is preferably 0.5～10 weight %, more preferably 0.75～8 weight %.Their concentration is low more, and it is just weak more that residue is removed effect, when being lower than 0.1 weight % especially a little less than.Concentration is high more, removes that effect is just high more, the life-span prolongs, but from the viewpoint of relative costs effect, is preferably below the 10 weight %.

By further removing in the liquid the neutral organic compound that adds fluorine compounds and contain oxygen atom that can coordination on Cu, can improve the effect of removing the residue that on the sidewall of the pattern that forms on the interlayer dielectrics such as Low-k film, adheres at residue.This residue is except Cu sex change beyond the region of objective existence, barrier film and Low-k films such as SiN, imbed agent etc. in dry ecthing by sputter, contain Si and organic substance sometimes.But,, when the Cu oxide is the main composition thing,, utilizes residue of the present invention to remove liquid and also can remove this residue even do not add fluorine compounds usually even in residue, contain Si and organic substance.In addition, the interlayer dielectrics such as Low-k film that are subjected to plasma damage in dry process may be processed as design size ground easily by the fluorine compounds etching.Therefore, when this residue of worry is removed insufficient or can not removed,, can add the low amount of fluorinated compound in order to increase the higher effect of removing.

The concentration of fluorine compounds can be according to containing interlayer dielectric such as silicon fiml, Low-k film and because dry process is subjected to the kind and the amount of the interlayer dielectric of plasma damage suitably selects.

Remove in the liquid at residue, the preferred use level of fluorine compounds (concentration) is 0.001～5 weight %, more preferably 0.01～3 weight %.When the part that is subjected to plasma damage that suppresses interlayer dielectric at needs is removed liquid corrosion and is carved by residue of the present invention, preferably do not contain or on a small quantity (1 weight % is following) cooperate fluorine compounds.But if less than 0.001 weight %, the effect of removing residue will descend.

In addition, residue of the present invention remove in the liquid add described later containing can be on Cu during the neutral organic compound of the oxygen atom of coordination, the degree of dissociation of fluorine compounds reduces, so in order to bring into play effect identical when having only the aqueous solution, preferred a large amount of fluorine compounds that add.But if greater than 5 weight %, the part that is subjected to plasma damage of interlayer dielectric will be etched, can't process as design size ground.

Can be further remove and add the neutral organic compound that contains oxygen atom that can coordination on Cu in the liquid at residue of the present invention.This neutrality organic compound is preferably the neutral organic solvent with 2 above oxygen atoms or has the neutral organic solvent that contains oxygen atom of hydrophobic groups such as chain alkyl.These organic solvents have residue that raising adheres on the sidewall of the pattern that forms on the interlayer dielectrics such as Low-k film and interlayer dielectric substrate surface residue remove effect, and have the antiseptic effect of Cu.Wherein, so-called neutral organic solvent is represented the proton property supplied with solvent (acid flux material) and protophilia solvent (basic solvent) solvent in addition.

As this neutrality organic compound, can enumerate ester classes such as poly-carbonyl class, hydroxyl ketone, carbonic ester, cyclic ester, keto ester, hydroxy ester (oxyester), alkoxy ester; Alcohols such as monohydric alcohol, polyalcohol, alkoxyl alcohol; Polyethers etc.

As poly-carbonyl class, for example, can enumerate 2,3-diacetyl, 2,4-pentanedione, methyl-glyoxal etc.Preferred 2,3-diacetyl, 2,4-pentanedione.

As the hydroxyl ketone, for example, can enumerate 3-hydroxy-2-butanone, pyruvic alcohol, diacetone alcohol etc.Preferred 3-hydroxy-2-butanone, pyruvic alcohol.

As the ester class, for example, can enumerate carbonic esters such as dimethyl carbonate, diethyl carbonate; Cyclic esters such as propene carbonate, ethylene carbonate, gamma-butyrolacton; Keto ester such as methyl acetoacetate, ethyl acetoacetate; Hydroxy esters such as methyl lactate, ethyl lactate, butyl lactate; Alkoxy ester such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethylether acetate, ethylene glycol mono-n-butyl ether acetic acid esters, diethylene glycol monomethyl ether acetic acid esters, acetate diethylene glycol monoethyl ether, acetate diglycol monotertiary n-butyl ether, ethylene acetate (oxalic acid ethyl), propylene glycol methyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate etc.

Preferably enumerate propene carbonate, gamma-butyrolacton, oxalic acid ethyl, PGMEA, methyl acetoacetate, ethyl acetoacetate, ethyl lactate etc.

As alcohols, for example, can enumerate the monohydric alcohol that isopropyl alcohol, 1-butanols, the tert-butyl alcohol, isobutanol etc. have hydrophobic groups such as long-chain (for example C3～6) alkyl; Ethylene glycol, diethylene glycol (DEG), triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, poly-(propylene glycol), glycerol, 2-amino-2-ethyl-1, ammediol, 2-amino-2-methyl-1, ammediol, 1, the 2-cyclohexanediol, 2,2-dimethyl-1, ammediol, 2,5-dimethyl-2, the 5-hexylene glycol, 2,3-naphthalene glycol, 1, the 2-butanediol, 1, the 3-butanediol, 1, the 4-butanediol, 2-butine-1, the 4-glycol, the 2-butene-1, the 4-glycol, 1, ammediol, 1, the 2-propylene glycol, DL-1, the 2-hexylene glycol, 2, the 5-hexylene glycol, 1, the 2-Benzenediol, 2, the 4-pentanediol, 2-methyl-2, polyalcohols such as 4-pentanediol; Alkoxyl alcohols such as glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, ethyleneglycol monophenylether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diglycol monotertiary isobutyl ether, diglycol monotertiary n-butyl ether, diglycol monotertiary benzylic ether, diglycol monotertiary hexyl ether, diglycol monotertiary benzylic ether, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol list dodecyl ether, heptandiol list dodecyl ether, poly glycol monomethyl ether.

Preferably enumerate isopropyl alcohol, 1-butanols, isobutanol, diethylene glycol (DEG), dipropylene glycol, triethylene glycol, tetraethylene glycol etc.

As polyethers, for example, can enumerate dimethoxymethane, diethoxymethane, dimethoxy-ethane, dimethoxy propane, glycol dimethyl ether, Ethylene Glycol Methyl ethylether, ethylene glycol diethyl ether, ethylene glycol bisthioglycolate n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol (DEG) methyl ethyl ether, diethyl carbitol, diethylene glycol (DEG) di-n-butyl ether, triglyme, triethylene glycol ethyl-methyl ether, triethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, Polyethylene glycol dimethyl ether etc.

Preferably enumerate glycol dimethyl ether, diethylene glycol dimethyl ether, diethyl carbitol, triglyme, tetraethylene glycol dimethyl ether etc.

In above-mentioned neutral organic compound, preferred 2, the 3-diacetyl, 2, the 4-pentanedione, acetylacetone,2,4-pentanedione, 3-hydroxy-2-butanone, propene carbonate, gamma-butyrolacton, the ethylene glycol mono-n-butyl ether acetic acid esters, the acetate diethylene glycol monoethyl ether, acetate diglycol monotertiary n-butyl ether, ethylene acetate (oxalic acid ethyl), propylene glycol methyl ether acetate (PGMEA), isopropyl alcohol, the 1-butanols, the tert-butyl alcohol, isobutanol, diethylene glycol (DEG), dipropylene glycol, triethylene glycol, tetraethylene glycol, glycerol, 2,2-dimethyl-1, ammediol, 1, ammediol, 2-methyl-2, the 4-pentanediol, ethylene glycol mono-n-butyl ether, the glycol monomethyl phenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, the diglycol monotertiary n-butyl ether, triethylene glycol monomethyl ether, the triethylene glycol monobutyl ether, the tripropylene glycol monomethyl ether, dimethoxymethane, glycol dimethyl ether, diethylene glycol dimethyl ether, diethyl carbitol, triglyme, tetraethylene glycol dimethyl ether, methyl acetoacetate, ethyl acetoacetate, ethyl lactate.

More preferably 2,3-diacetyl, 2,4-pentanedione, 3-hydroxy-2-butanone, propene carbonate, gamma-butyrolacton, acetate diethylene glycol monoethyl ether, ethylene acetate (oxalic acid ethyl), propylene glycol methyl ether acetate (PGMEA), isopropyl alcohol, 1-butanols, isobutanol, diethylene glycol (DEG), dipropylene glycol, triethylene glycol, tetraethylene glycol, glycol dimethyl ether, diethylene glycol dimethyl ether, diethyl carbitol, triglyme, tetraethylene glycol dimethyl ether, methyl acetoacetate, ethyl acetoacetate, ethyl lactate.

Preferred especially 2,3-diacetyl, 3-hydroxy-2-butanone, propene carbonate, acetate diethylene glycol monoethyl ether, ethylene acetate (oxalic acid ethyl), propylene glycol methyl ether acetate (PGMEA), isopropyl alcohol, diethylene glycol (DEG), triethylene glycol, tetraethylene glycol, glycol dimethyl ether, diethylene glycol dimethyl ether, triglyme, methyl acetoacetate, ethyl acetoacetate, ethyl lactate.

Remove in the liquid at residue, contain and on Cu, the use level (concentration) of the neutral organic compound of the oxygen atom of coordination to be generally 0.1～60 weight %, be preferably 2～40 weight %.

Remove in the liquid at residue of the present invention and can also add surfactant.Surfactant is used for hydrophobic interlayer dielectric is increased wetability, prevents soup because the shape of pattern and the situation that can not spread all over etc.Its kind can be cationic, anionic, nonionic etc., is not particularly limited.Use level (concentration) is 0.00001～5 weight %, is preferably 0.0001～3 weight %.If less than 0.00001 weight %, the surface activity effect is little; Even if greater than 5 weight %, its effect does not change yet.

Remove in the liquid at residue, the ratio that residue of the present invention is removed water contained in the liquid is generally about 40～99.5 weight %, is preferably about 60～99 weight %, can be according to the use level decision of the composition beyond the water.

The pH that residue of the present invention is removed liquid is 4～9.If pH less than 4, corrodes Cu easily; If pH greater than 9, will cause damage to the Low-k film.PH is preferably 4～7.Aldehydic acid when pH passes through preparation salt and/or the component adjustment of ketone acid and alkali.

For example; when residue is removed in the salt that liquid contains the salt that is selected from ketone acid, ketone acid and aldehydic acid at least a kind, Cu surface protectant and water; at least a kind the use level that is selected from the salt of the salt of ketone acid, ketone acid and aldehydic acid is (to be preferably about 0.5～20 weight %) about 0.1～35 weight %; the use level of Cu surface protectant is (to be preferably that 0.2ppm～500ppm), pH is about 4～8 (being preferably about 5～7) about 0.1ppm～1000ppm.

In addition; removing liquid at residue contains and is selected from ketone acid; in the salt of ketone acid and the salt of aldehydic acid at least a kind; neutral organic compound with oxygen atom that can coordination on the Cu oxide; when Cu surface protectant and water; be selected from ketone acid; at least a kind use level in the salt of ketone acid and the salt of aldehydic acid is (to be preferably about 1～10 weight %) about 0.5～20 weight %; the use level of neutral organic compound is (to be preferably about 2～40 weight %) about 0.1～60 weight %; the use level of Cu surface protectant is (to be preferably that 0.5ppm～1000ppm), pH is about 4～8 (being preferably about 5～7) about 0.2ppm～2000ppm.

In addition; when residue is removed in the salt that liquid contains the salt that is selected from ketone acid, ketone acid and aldehydic acid at least a kind, multi-carboxylate, Cu surface protectant and water; at least a kind the use level that is selected from the salt of the salt of ketone acid, ketone acid and aldehydic acid is (to be preferably about 0.5～5 weight %) about 0.1～10 weight %; multi-carboxylate's use level is (to be preferably about 0.5～8 weight %) about 0.1～10 weight %; the use level of Cu surface protectant is (to be preferably that 1ppm～500ppm), pH is about 4～6 (being preferably about 5～6) about 0.5ppm～1000ppm.

In addition; removing liquid at residue contains and is selected from ketone acid; in the salt of ketone acid and the salt of aldehydic acid at least a kind; the multi-carboxylate; neutral organic compound with oxygen atom that can coordination on the Cu oxide; when Cu surface protectant and water; be selected from ketone acid; at least a kind use level in the salt of ketone acid and the salt of aldehydic acid is (to be preferably about 0.5～5 weight %) about 0.1～10 weight %; multi-carboxylate's use level is (to be preferably about 0.5～8 weight %) about 0.1～10 weight %; the use level of neutral organic compound is (to be preferably about 2～40 weight %) about 0.1～60 weight %; the use level of Cu surface protectant is (to be preferably that 1ppm～2000ppm), pH is about 4～6 (being preferably about 5～6) about 0.5ppm～3000ppm.

Residue is removed liquid (B)

The liquid of removing of the present invention is characterised in that, contains to form strong acid (below be also referred to as " strong acid "), multi-carboxylate, Cu surface protectant and the water of complex or chelate as basic composition with Cu.By further being added with organic compounds, surfactant, fluorine compounds, anticracking additive, antioxidant etc., can increase more excellent function.

The kind of Cu surface protectant and use level thereof can be enumerated above-mentioned item.Particularly, the strong acid that can form complex or chelate with Cu is that 25 ℃ pKa is the Bronsted acid of (be preferably below 2, more preferably 0～2) below 3, supplies with hydrogen ion H ⁺, and form the reagent (part) of chelate or complex with Cu, have the function of the residue after the dry process of removing.

As object lesson, can enumerate Halogen carboxylic acids such as chloroacetic acid, dichloroacetic acid, trichloroacetic acid, α-chloro-butyric acid, β-chloro-butyric acid, γ-chloro-butyric acid, a fluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, hydrobromic acid, perchloric acid, sulfuric acid, oxalic acid, malonic acid, tartaric acid, citric acid etc.Wherein, preferred oxalic acid, malonic acid, citric acid, trifluoroacetic acid, hydrobromic acid, perchloric acid, more preferably oxalic acid, malonic acid, citric acid and trifluoroacetic acid.

The multi-carboxylate can reduce the damage to the Low-k film, and interacts with strong acid, the effect of the residue after giving the effect that prevents the Cu corrosion and removing the dry process that contains Cu.Particularly polycarboxylic amine salt suppresses the effect height of Cu surface checking.

As the multi-carboxylate, for example, can enumerate the salt that alkali such as polycarboxylic acid such as malonic acid, succinic acid, glutaric acid, adipic acid, malic acid, tartaric acid, diammonium hydrogen citrate, ammonium dihydrogen citrate, citric acid and ammonia, azanol, primary amine, secondary amine or tertiary amine, quaternary ammonium, alkanolamine, polyamine form.Preferably enumerate the salt that alkali such as polycarboxylic acid such as malonic acid, diammonium hydrogen citrate, ammonium dihydrogen citrate, citric acid and ammonia, primary amine, secondary amine or tertiary amine, quaternary ammonium, alkanolamine, polyamine form.

More specifically, can enumerate malonic acid, diammonium hydrogen citrate, ammonium dihydrogen citrate, polycarboxylic ammonium salt such as citric acid, methylamine salt, ethylamine salt, propylamine salt, butylamine salt, dimethylamine salt, the diethyl amine salt, the front three amine salt, triethylamine salt, ethanolamine salt, diethanolamine salt, triethanolamine salt, the diisopropanol amine salt, triisopropanolamine salt, the isopropyl alcohol amine salt, the normal propyl alcohol amine salt, N, N-dimethyl ethanol amine salt, N-methyl ethanol amine salt, N methyldiethanol amine salt, N-acetyl ethanonlamine salt, N-ethyl hexanol amine salt, propane diamine salt, trien salt, Tetramethylammonium hydroxide salt, choline salt etc.

Wherein, the most preferably ammonium salt of malonic acid, methylamine salt, ethylamine salt, Tetramethylammonium hydroxide salt or choline salt; The methylamine salt of diammonium hydrogen citrate, ethylamine salt, Tetramethylammonium hydroxide salt or choline salt; The methylamine salt of ammonium dihydrogen citrate, ethylamine salt, Tetramethylammonium hydroxide salt or choline salt; Ammonium salt, methylamine salt, ethylamine salt, Tetramethylammonium hydroxide salt or choline salt with citric acid.

In addition, residue is removed contained can being preferably about 0.3～1 with the ratio (strong acid/multi-carboxylate) of molal quantity and multi-carboxylate's molal quantity that Cu forms the strong acid of complex or chelate in the liquid, is preferably 0.35～0.8 especially.This is because 0.3 when following, corrode Cu easily, 1 when above, removes the ability drop of the residue after the dry process.

Can remove at residue of the present invention and be added with organic compounds (particularly water-soluble organic compounds) in the liquid.This organic compound can reduce the corrosion to Cu that is caused by strong acid, gives the effect of removing the residue after the dry processes such as residue of residue that adheres on the sidewall of the pattern that forms on the interlayer dielectrics such as Low-k film and interlayer dielectric substrate surface.

As organic compound, can enumerate hydrophily or water miscible neutral organic compound, for example, preferably poly-carbonyl class, hydroxyl ketone, ester class, the alcohols more than the C3, the aldehydes more than the C3, polyethers, sulfone class etc.

As poly-carbonyl class, for example, can enumerate 2,3-diacetyl, 2,4-pentanedione, methyl-glyoxal, acetylacetone,2,4-pentanedione etc.Preferred 2,3-diacetyl, 2,4-pentanedione.

As the ester class, for example, can enumerate monocarboxylic esters such as methyl acetate, ethyl acetate, methyl propionate, ethyl propionate; Polycarboxylates such as dimethyl oxalate, diethy-aceto oxalate, dimethyl malenate, diethyl malonate, dimethyl succinate; Carbonic ester such as dimethyl carbonate, diethyl carbonate; Cyclic esters such as propene carbonate, ethylene carbonate, gamma-butyrolacton; Keto ester such as methyl acetoacetate, ethyl acetoacetate; Hydroxy esters such as methyl lactate, ethyl lactate, butyl lactate; Alkoxy ester such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethylether acetate, ethylene glycol mono-n-butyl ether acetic acid esters, diethylene glycol monomethyl ether acetic acid esters, acetate diethylene glycol monoethyl ether, acetate diglycol monotertiary n-butyl ether, ethylene acetate (oxalic acid ethyl), propylene glycol methyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate etc.Preferably enumerate propene carbonate, gamma-butyrolacton, oxalic acid ethyl, PGMEA, methyl acetoacetate, ethyl acetoacetate, ethyl lactate etc.

As the alcohols more than the C3, for example, can enumerate the monohydric alcohol that isopropyl alcohol, 1-butanols, the tert-butyl alcohol, isobutanol etc. have hydrophobic groups such as long-chain (for example C3～6) alkyl; Ethylene glycol, diethylene glycol (DEG), triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, poly-(propylene glycol), glycerol, 2-amino-2-ethyl-1, ammediol, 2-amino-2-methyl-1, ammediol, 1, the 2-cyclohexanediol, 2,2-dimethyl-1, ammediol, 2,5-dimethyl-2, the 5-hexylene glycol, 2,3-naphthalene glycol, 1, the 2-butanediol, 1, the 3-butanediol, 1, the 4-butanediol, 2-butine-1, the 4-glycol, the 2-butene-1, the 4-glycol, 1, ammediol, 1, the 2-propylene glycol, DL-1, the 2-hexylene glycol, 2, the 5-hexylene glycol, 1, the 2-Benzenediol, 2, the 4-pentanediol, 2-methyl-2, polyalcohols such as 4-pentanediol; Alkoxyl alcohols such as glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, glycol monomethyl phenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diglycol monotertiary isobutyl ether, diglycol monotertiary n-butyl ether, diglycol monotertiary benzylic ether, diglycol monotertiary hexyl ether, diglycol monotertiary benzylic ether, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol list dodecyl ether, heptandiol list dodecyl ether, poly glycol monomethyl ether.Preferred isopropyl alcohol, 1-butanols, isobutanol, diethylene glycol (DEG), dipropylene glycol, triethylene glycol, tetraethylene glycol etc.

As the aldehydes more than the C3, for example, can enumerate propionic aldehyde, butyraldehyde, valeral etc.

As polyethers, for example, can enumerate dimethoxymethane, diethoxymethane, dimethoxy-ethane, dimethoxy propane, glycol dimethyl ether, Ethylene Glycol Methyl ethylether, ethylene glycol diethyl ether, ethylene glycol bisthioglycolate n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol (DEG) methyl ethyl ether, diethyl carbitol, diethylene glycol (DEG) di-n-butyl ether, triglyme, triethylene glycol ethyl-methyl ether, triethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, Polyethylene glycol dimethyl ether etc.Preferably enumerate glycol dimethyl ether, diethylene glycol dimethyl ether, diethyl carbitol, triglyme, tetraethylene glycol dimethyl ether etc.

As the sulfone class, for example, can enumerate sulfolane, dimethyl sulfone etc.

In the above-mentioned organic compound, preferred 2, the 3-diacetyl, 2, the 4-pentanedione, 3-hydroxy-2-butanone, propene carbonate, gamma-butyrolacton, ethylene acetate (oxalic acid ethyl), propylene glycol methyl ether acetate (PGMEA), isopropyl alcohol, the 1-butanols, isobutanol, diethylene glycol (DEG), dipropylene glycol, triethylene glycol, tetraethylene glycol, the acetate diethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethylether acetate, glycol dimethyl ether, diethylene glycol dimethyl ether, diethyl carbitol, triglyme, tetraethylene glycol dimethyl ether, methyl acetoacetate, ethyl acetoacetate, ethyl lactate.

Remove in the liquid at residue, the use level of organic compound (concentration) is below the 60 weight %, is preferably 0.5～60 weight %, and more preferably 2～40 weight % are preferably 3～30 weight % especially.

Further add fluorine compounds in the liquid by removing, can improve the effect of removing the residue that on the sidewall of the pattern that forms on the interlayer dielectrics such as Low-k film, adheres at residue.This residue is except Cu sex change beyond the region of objective existence, barrier film and Low-k films such as SiN, imbed agent etc. in dry ecthing by sputter, contain Si and organic substance sometimes.But,, when the Cu oxide is the main composition thing,, utilizes residue of the present invention to remove liquid and also can remove this residue even do not add fluorine compounds usually even in residue, contain Si and organic substance.In addition, the interlayer dielectrics such as Low-k film that are subjected to plasma damage in dry process may be processed as design size ground easily by the fluorine compounds etching.Therefore, when this residue of worry is removed insufficient or can not removed,, can add the low amount of fluorinated compound in order to append the higher effect of removing.

Remove in the liquid at residue, the preferred use level of fluorine compounds (concentration) is 0.001～5 weight %, more preferably 0.01～3 weight %.The part that is subjected to plasma damage that suppresses interlayer dielectric at needs is by of the present invention when removing liquid corrosion and carving, preferably do not contain or on a small quantity (1 weight % is following) cooperate fluorine compounds.But if less than 0.001 weight %, the effect of removing residue will descend.Particularly remove in the liquid at the residue that contains above-mentioned strong acid, fluorine compounds are preferably below the 1 weight %, in addition, remove in the liquid at the residue that contains the multi-carboxylate, and fluorine compounds are preferably below the 5 weight %.

Remove in the liquid at residue, the ratio that residue of the present invention is removed water contained in the liquid is generally about 40～99.5 weight %, is preferably about 70～99 weight %, can be according to the use level decision of the composition beyond the water.

The pH that removes liquid of the present invention is 4～7.If the Low-k film that pH less than 4, sustains damage in dry process surface sex change easily; If p H greater than 7, corrodes Cu easily.PH is preferably 4～6.5.PH is by strong acid and multi-carboxylate, as required the component adjustment of organic compound.

For example; removing liquid at residue contains can form the strong acid, multi-carboxylate, Cu surface protectant of complex or chelate and water with Cu the time; the use level of this strong acid is (to be preferably about 0.3～3 weight %) about 0.1～5 weight %; multi-carboxylate's use level is (to be preferably about 0.5～10 weight %) about 0.1～20 weight %; the use level of Cu surface protectant is (to be preferably that 1ppm～500ppm), pH is about 4～6.5 (being preferably about 4～6) about 0.5ppm～1000ppm.The molal quantity of strong acid is about 0.3～1 (being preferably about 0.35～0.8) with respect to the ratio of multi-carboxylate's molal quantity.

In addition; remove liquid at residue and contain the strong acid that can form complex or chelate with Cu; the multi-carboxylate; organic compound; when Cu surface protectant and water; the use level of this strong acid is (to be preferably about 0.3～3 weight %) about 0.1～5 weight %; this multi-carboxylate's use level is (to be preferably about 0.75～10 weight %) about 0.5～20 weight %; the use level of organic compound is that 0.5～60 weight % (is preferably 2～40 weight %; 3～30 weight % more preferably); the use level of Cu surface protectant is (to be preferably that 1ppm～2000ppm), pH is about 4～7 (being preferably about 4～6) about 0.5ppm～3000ppm.The molal quantity of strong acid is about 0.3～1 (being preferably about 0.35～0.8) with respect to the ratio of multi-carboxylate's molal quantity.

Residue is removed liquid (C)

Residue of the present invention is removed liquid and is characterised in that, contains that have more than 2 can be at the neutral organic compound of the oxygen atom of coordination on the Cu (below be also referred to as " neutral organic compound ") and/or the monobasic alcohol and water more than the C4 as basic composition.

As neutral organic compound, can be the organic compound that Cu is had the neutrality of the oxygen coordination site more than 2, so-called neutral, the expression proton property supplied with solvent (acidity) and protophilia solvent (alkalescence) character in addition.For example, can enumerate poly-carbonyl class, ketols, hydroxy ester class, diester class, keto ester class, lactone, carbonates, polyethers, glycols, alkylene glycol mono ethers, aklylene glycol diester class, aklylene glycol ether-ether class, polyalkylene glycols, polyalkylene glycol mono ethers, PAG diester class, polyalkylene glycol ethers ester class etc.

As ketols, for example, can enumerate 3-hydroxy-2-butanone, diacetone alcohol, pyruvic alcohol etc.Wherein preferred 3-hydroxy-2-butanone.

As polyethers, for example, can enumerate glycol dialkyl ether (dimethoxymethane, dimethoxy-ethane, diethoxymethane, the Ethylene Glycol Methyl ethylether, dimethoxy-ethane, diethoxymethane, diethoxyethane, the ethylene glycol bisthioglycolate n-butyl ether, dimethoxy propane etc.), PAG dialkyl ether (diethylene glycol dimethyl ether, the diethylene glycol (DEG) methyl ethyl ether, diethyl carbitol, the diethylene glycol (DEG) di-n-butyl ether, triglyme, triethylene glycol ethyl-methyl ether, the triethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, the tetraethylene glycol diethyl ether, Polyethylene glycol dimethyl ether etc.) etc.

Wherein, preferred dimethoxy-ethane, diethylene glycol dimethyl ether, diethyl carbitol, triglyme, tetraethylene glycol dimethyl ether.

As the polyalkylene glycol mono ethers, for example, can enumerate diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diglycol monotertiary isobutyl ether, diglycol monotertiary n-butyl ether, diglycol monotertiary benzylic ether, diglycol monotertiary hexyl ether, diglycol monotertiary benzylic ether, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol list dodecyl ether, heptandiol list dodecyl ether, poly glycol monomethyl ether etc.Wherein, alkoxyl alcohols such as preferred diethylene glycol monomethyl ether, diethylene glycol monoethyl ether.

In the above-mentioned neutral organic compound, also have and have the compound that in the aqueous solution, is subjected to the ester group of hydrolysis easily.For example, can enumerate hydroxy ester class, diester class, keto ester class, lactone, carbonates, aklylene glycol diester class, aklylene glycol ether-ether class, PAG diester class and polyalkylene glycol ethers ester class.For such ester class, preferably further remove in the liquid to add and be used for neutralizing hydrolysis and generate H at residue ⁺Water-soluble alkali or be used to control the H of generation ⁺The multi-carboxylate.Contain Cu by adding the multi-carboxylate, increasing _xThe antiseptic effect of removing effect and Cu of O residue.When using amine and when adding polycarboxylic amine salt, prevent that the effect of Cu surface checking also is enhanced as water-soluble alkali, thus preferred.

As the multi-carboxylate, for example, can enumerate the salt that alkali such as polycarboxylic acid such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, malic acid, tartaric acid, diammonium hydrogen citrate, ammonium dihydrogen citrate, citric acid and ammonia, azanol, primary amine, secondary amine or tertiary amine, quaternary ammonium, alkanolamine, polyamine form.Preferably enumerate the salt that alkali such as polycarboxylic acid such as malonic acid, diammonium hydrogen citrate, ammonium dihydrogen citrate, citric acid and ammonia, primary amine, secondary amine or tertiary amine, quaternary ammonium, polyamine form.

More specifically, can enumerate malonic acid, diammonium hydrogen citrate, ammonium dihydrogen citrate, polycarboxylic ammonium salt such as citric acid, methylamine salt, ethylamine salt, propylamine salt, butylamine salt, dimethylamine salt, the diethyl amine salt, the front three amine salt, triethylamine salt, ethanolamine salt, diethanolamine salt, triethanolamine salt, the diisopropanol amine salt, triisopropanolamine salt, the isopropyl alcohol amine salt, the normal propyl alcohol amine salt, N, N-dimethyl ethanol amine salt, N-methyl ethanol amine salt, N methyldiethanol amine salt, N-acetyl ethanonlamine salt, N-ethyl hexanol amine salt, propane diamine salt, Tetramethylammonium hydroxide salt and choline salt.

The multi-carboxylate can use with the form of crystallization, also can use the aqueous solution that mixes these bronsted lowry acids and bases bronsted lowry neutralizations and generate in water.Remove in the liquid at residue, multi-carboxylate's use level (concentration) is 0.1～15 weight %, is preferably 0.5～10 weight %, more preferably 0.75～8 weight %.

Can also add perchlorate.As perchlorate, be and the salt that is selected from least a kind of formation in ammonia, azanol, primary amine, secondary amine or tertiary amine, quaternary ammonium and the polyamine to enumerate ammonium perchlorate, Thyronorman's amine salt, perchloric acid propane polyamine salt, perchloric acid trien salt etc.Wherein, preferred ammonium perchlorate.

In addition, residue of the present invention is removed liquid and is substantially free of fluorine compounds, but, for example under the situation of using the monohydric alcohol more than the C4 and situation, can further add fluorine compounds as neutral organic compound use ketols, hydroxy ester class, diester class, keto ester class, lactone, carbonates, aklylene glycol diester class, aklylene glycol ether-ether class, PAG diester class, polyalkylene glycol ethers ester class etc.

By adding fluorine compounds, can improve the effect of removing the residue that on the sidewall of the pattern that forms on the interlayer dielectrics such as Low-k film, adheres to.This residue is except Cu sex change beyond the region of objective existence, barrier film and Low-k films such as SiN, imbed agent etc. in dry ecthing by sputter, contain Si and organic substance sometimes.But,, when the Cu oxide is the main composition thing,, utilizes residue of the present invention to remove liquid and also can remove this residue even do not add fluorine compounds usually even in residue, contain Si and organic substance.In addition, the interlayer dielectrics such as Low-k film that are subjected to plasma damage in dry process may be processed as design size ground easily by the fluorine compounds etching.Therefore, when this residue of worry is removed insufficient or can not removed,, can add the low amount of fluorinated compound in order to append the higher effect of removing.

Remove in the liquid at residue of the present invention and can also add surfactant.Surfactant is used for hydrophobic interlayer dielectric is increased wetability, prevents the situation that soup can not spread all over owing to the shape of pattern.Its kind can be cationic, anionic, nonionic etc., is not particularly limited.Concentration is 0.00001～5 weight %, is preferably 0.0001～3 weight %.If less than 0.00001 weight %, the surface activity effect is little; Even if greater than 5 weight %, its effect does not change yet.

The pH that residue of the present invention is removed liquid is 4～7.If pH is below 4, corrode Cu easily; If pH greater than 7, causes damage to the Low-k film sometimes.PH is preferably 4～6.PH adjusts by alkali.

Residue of the present invention is removed the concrete example of liquid (C), can be listed below example.

For example; when residue is removed liquid and is contained neutral organic compound, Cu surface protectant and water; the use level of neutral organic compound is (to be preferably about 3～20 weight %) about 0.1～60 weight %; the use level of Cu surface protectant is (to be preferably that 0.5ppm～1000ppm), pH is about 4～7 (being preferably about 4～6) about 0.2ppm～2000ppm.

In addition; when residue is removed liquid and is contained monohydric alcohol more than the C4, Cu surface protectant and water; the use level of the monohydric alcohol that C4 is above is (to be preferably about 2～5 weight %) about 1～10 weight %; the use level of Cu surface protectant is (to be preferably that 0.5ppm～500ppm), pH is about 4～7 (being preferably about 5～7) about 0.2ppm～1000ppm.

In addition; when residue is removed liquid and is contained neutral organic compound, water-soluble alkali, Cu surface protectant and water; the use level of neutral organic compound is (to be preferably about 1～10 weight %) about 0.1～20 weight %; the use level of water-soluble alkali is (to be preferably about 0.1～3 weight %) about 0.05～5 weight %; the use level of Cu surface protectant is (to be preferably that 0.5ppm～1000ppm), pH is about 4～7 (being preferably about 4～6) about 0.2ppm～2000ppm.

In addition; when residue is removed liquid and is contained neutral organic compound, multi-carboxylate, Cu surface protectant and water; the use level of neutral organic compound is (to be preferably about 3～20 weight %) about 0.1～60 weight %; multi-carboxylate's use level is (to be preferably about 0.5～5 weight %) about 0.1～10 weight %; the use level of Cu surface protectant is (to be preferably that 1ppm～2000ppm), pH is about 4～7 (being preferably about 4～6) about 0.5ppm～3000ppm.

Residue is removed liquid (D)

Residue of the present invention is removed liquid and is characterised in that it is the aqueous solution that contains perchlorate and water.

The kind of Cu surface protectant and use level thereof can be enumerated above-mentioned situation.Particularly, perchlorate can use at above-mentioned residue and remove the compound of enumerating in the liquid (C).Particularly, as perchlorate, be and the salt that is selected from least a kind of formation in ammonia, azanol, primary amine, secondary amine or tertiary amine, quaternary ammonium and the polyamine to enumerate ammonium perchlorate, Thyronorman's amine salt, perchloric acid propane polyamine salt, perchloric acid trien salt etc.Wherein, preferred ammonium perchlorate.

Remove in the liquid at the residue that contains perchlorate, can also contain enumerate in the soup (A) have more than 2 can be at the neutral organic compound of the oxygen atom of coordination on the Cu and/or the monohydric alcohol more than the C4.The effect of the residue after can making the effect of the corrosion that suppresses the Cu piece and Cu surface checking and removing dry process strengthens.And its use level also can adopt the use level of enumerating in the soup (C).

In addition, remove in the liquid, can also add water-soluble alkali, multi-carboxylate, surfactant, fluorine compounds, antioxidant, anticracking additive etc. at residue of the present invention.These for example can use residue to remove the material of enumerating in the liquid (C), and its use level also can adopt residue to remove the use level of enumerating in the liquid (C).

Remove the concrete example of liquid (D) as residue of the present invention, can be listed below example.

For example; when residue is removed liquid and is contained perchlorate, Cu surface protectant and water; the use level of perchlorate is (to be preferably about 0.3～5 weight %) about 0.1～10 weight %; the use level of Cu surface protectant is (to be preferably that 0.2ppm～500ppm), pH is about 4～7 (being preferably about 5～7) about 0.1ppm～1000ppm.

In addition; when residue is removed liquid and is contained perchlorate, neutral organic compound and/or the monohydric alcohol more than the C4, Cu surface protectant and water; the use level of perchlorate is (to be preferably about 0.3～5 weight %) about 0.1～10 weight %; the use level of the monohydric alcohol that neutral organic compound and/or C4 are above is (to be preferably about 2～40 weight %) about 0.5～60 weight %; the use level of Cu surface protectant is (to be preferably that 0.5ppm～1000ppm), pH is about 4～7 (being preferably about 5～7) about 0.2ppm～2000ppm.

In addition; remove liquid at residue and contain perchlorate; neutral organic compound; water-soluble alkali; when Cu surface protectant and water; the use level of perchlorate is (to be preferably about 0.3～5 weight %) about 0.1～10 weight %; the use level of neutral organic compound is (to be preferably about 2～30 weight %) about 0.5～40 weight %; the use level of water-soluble alkali is (to be preferably about 2～30 weight %) about 0.5～40 weight %; the use level of Cu surface protectant is (to be preferably that 0.5ppm～1000ppm), pH is about 4～7 (being preferably about 4～6) about 0.2ppm～2000ppm.

In addition; remove liquid at residue and contain perchlorate; neutral organic compound; the multi-carboxylate; when Cu surface protectant and water; the use level of perchlorate is (to be preferably about 0.3～5 weight %) about 0.1～10 weight %; the use level of neutral organic compound is (to be preferably about 2～40 weight %) about 0.5～60 weight %; multi-carboxylate's use level is (to be preferably about 0.75～10 weight %) about 0.5～20 weight %; the use level of Cu surface protectant is (to be preferably that 1ppm～2000ppm), pH is about 4～7 (being preferably about 4～6) about 0.5ppm～3000ppm.

Remove the object residue

Residue of the present invention is removed the object of liquid, mainly is the Cu oxide-film that be removed and the residue after the dry process and should protected Cu surface.

As the Cu oxide-film, the natural oxide film of Cu oxide-film that forms in the time of can being set forth in dry ecthing and/or ashing or the Cu that metal is generated by autoxidation when being exposed in the atmosphere owing to moving between the technology etc. etc.As their composition, comprise CuO, Cu mostly ₂O, Cu (OH) ₂Deng.

Residue after the dry process comprises: using Cu as conductive metal and in the wafer of film forming, the lip-deep Cu oxide-film of the Cu of Cu/Low-k multi-layer wiring structure and/or contain the Cu sex change thing of the Cu oxide that forms by dry ecthing and/or ashing.This residue is mainly attached to forming on the figuratum Cu distribution and the sidewall and the interlayer dielectric substrate surface of the pattern that forms on interlayer dielectrics such as Low-k film.The residue that forms on Cu is to comprise owing to dry ecthing and/or ashing, sustain damage oxidized and/or by the sex change thing residue of the mixture of the Cu oxide fluoridized and this Cu, resistance is increased.Because this Cu sex change thing comprises Cu oxide and Cu oxidized and/or that fluoridize, so it is similar to the insulating barrier of Cu oxide for resistance.

The residue that on the sidewall of the pattern that forms on the interlayer dielectrics such as Low-k film, adheres to, except Cu sex change beyond the region of objective existence, barrier film and Low-k films such as SiN, imbed agent etc. in dry ecthing by sputter, contain Si and organic substance sometimes.In addition, can infer the residue of interlayer dielectric substrate surface, at resist, the antireflection film that can't remove fully by ashing with imbed organic substance such as agent and use in the residue of technology of inorganic mask, contain when dry ecthing from the hole or the bottom of ditch is sudden a little Si and Cu sex change thing.

In this manual, so-called interlayer dielectric mainly is Low-k film and porous Low-k, for example, also comprises the silicon oxide layer (fsg film) that contains fluorine, the expression dielectric constant is about below 4, preferably is about below 3, is more preferably below 2.8, is more preferably the dielectric film below 2.6 greater than 1.The Low-k film mainly forms by coating or plasma CVD.

Particularly, the LKD of being called series (trade name, JSR society produce), HSG series (trade name, Hitachi change into society and produce), Nanoglass (trade name, Honeywell society produce), IPS (trade name, catalyst change into society and produce), Z are arranged ₃M (trade name, Dow Corning society produces), XLK (trade name, Dow Corning society produces), FOx (trade name, Dow Corning society produces), Orion (trade name, Tricon society produces), NCS (trade name, catalyst changes into society and produces), SiLK, porous-SiLK (trade name, the production of Dow Corning society) etc. inorganic SOG (HSG: the silane sesquioxyalkane), organic sog film (msq film: the methyl silsesquioxane film), with polyene propyl ether etc. is the coated film of the organic polymer films of main component, with Black Diamond (trade name, Applied Materials society produces), Coral (trade name, Novellus society produces), Aurora (trade name, ASM society produces) for the plasma CVD film of representative etc., but be not limited to these.

As resist, can enumerate KrF (Krypton F), ArF, F ₂Resist etc., but be not limited to these.

Imbedding agent is the organic compound that has the antireflection film function concurrently mostly.

Removing of residue after II.Cu oxide and/or the dry process

Residue removal method of the present invention mainly is in the formation operation of structures such as embedding, two embeddings and capacitor arrangement, removes the residue that exists on the semiconductor substrate after the dry process (dry ecthing and/or ashing).Particularly, use above-mentioned residue to remove liquid, remove the residue that on semiconductor substrate, exists after the dry process with Cu/Low-k multi-layer wiring structure.

The present invention also provides the manufacture method of semiconductor equipment.This manufacture method is characterised in that, comprising: (1) to have Cu (Cu) as wiring material, have film having low dielectric constant (Low-k film) carries out dry ecthing and/or ashing as the semiconductor substrate of interlayer dielectic operation; (2) make the semiconductor substrate after handling by above-mentioned (1) remove the operation that liquid contacts with above-mentioned residue.

And, after forming the Low-k film on the substrate, as required, on the Low-k film, form dielectric film barrier layers such as SiN, SiC, TaN film, but also can carry out etching to this SiN, SiC, TaN film etc. with the Low-k film.

Remove liquid as the semiconductor substrate of object being treated with residue and contact by making, carry out the processing that residue is removed.Remove the method that liquid contacts with residue, so long as can remove residue after Cu oxide and/or the dry process, the burn into that suppresses Cu do not have the method for essence damage to get final product to the Low-k film, be not particularly limited, can suitably set according to kind and temperature that residue is removed liquid.As contact method, can adopt various contact methods, a large amount of object being treated (wafer) in the box of for example will packing into is immersed in batch type in the groove that stores soup, drenches one chip that soup cleans, utilizes sprayer to the capable atomizing of cleaning of object being treated (wafer) spray soup spirt etc. from object being treated (wafer) upper punch of rotation.

The temperature that residue is removed liquid for example is about 10～60 ℃, to be preferably about 15～40 ℃.Be not defined time of contact yet, can suitably select, for example can illustration about 0.5 minute～60 minutes, be preferably 1 minute～40 minutes.

In addition, under the situation of batch type, can as required wafer dipping residue under agitation be removed in the liquid.Mixing speed is also unqualified, can suitably select.When refuse is difficult to peel off, for example, object being treated can be immersed in residue and remove in the liquid, carry out ultrasonic cleansing.

The method of removing of Cu oxide of the present invention can be further cleaned with pure water and is removed the wafer behind the residue after Cu oxide and/or the dry process.By this clean operation, the residue of the Cu of containing surface protectant of the present invention can be removed the liquid flush away.

Use the residue of the Cu of containing surface protectant of the present invention to remove semiconductor substrate after liquid carries out the removing of residue after Cu oxide and/or the dry process; for example; according to (for example forming customary ways such as Cu distribution; write the method for putting down in writing in calendar year 2001 in " semiconductor CMP technology is detailed to be said " (Details says half Guide body CMP Ji Intraoperative), Toi Shunro), be processed into various semiconductor devices (equipment) processing.

In addition; attached to the surface protectant on Cu surface, by in the follow-up technology such as the sputter after cleaning or in the disengaging technology that newly adds, under inert gas or vacuum; be heated to (preferred about 200～300 ℃) more than 180 ℃, the Cu surface protectant is broken away from from semiconductor substrate.

Embodiment

Below represent embodiment, clear and definite feature of the present invention.The present invention is not limited by these embodiment.

For oxidation, Cu be full of cracks and the shaggy degree of Cu of the Cu after studying the residue that uses after the dry process contain the Cu surface protectant and removing liquid and handle, use the wafer of the test pattern that has the two embedded structures of Cu/Low-k that form by boring technology earlier.The Low-k film of the two embedded structures of Cu/Low-k is the SiOC films that form by plasma CVD, and the dielectric film barrier layer is the SiN film.Residue after the dry process is present at the bottom of the via mostly, can see a little in sidewalls and Low-k substrate surface.The Cu surface sustains damage in dry process, is easily because soup is handled the sample that produces be full of cracks and rough surface etc.

This wafer that has a test pattern (about 600rpm) under 25 ℃, stirring condition is immersed in the soup shown in embodiment and the comparative example 1～3 minute, and then with flowing water flushing, the drying of ultra-pure water, the residue that carries out after the dry process is removed processing.

After this residue is removed processing, 12 vias are observed state and the cross sectional shape that the residue after the dry processes is removed with electron microscope (SEM).And, have or not be full of cracks and Cu rough surface state in order to judge the Cu surface, observe 60 vias from the top with electron microscope (SEM).Also utilize SEM to observe the cross section as required.

In addition, in order to study indiscoverable damage in the evaluation of using the wafer of having test pattern to Cu and Low-k film, to carry out pattern-free wafer (blanketwafer) after the film forming to them and be immersed in the soup of embodiment and comparative example 10 minutes, obtain their etching speed.To the variation of Low-k film research surface state, the contact angle before and after the mensuration soup dipping also compares.When the variation of contact angle is big, can obtain breaking away from the dependency relation of analyzing water adsorption amount increase in (TDS) heating up.That is the most surperficial variation of the variation of contact angle reflection Low-k film.In addition, contact angle uses the contact angle meter to measure.

Further will in soup, remain on (25 ℃, 40%RH) in the atmosphere by the pattern-free wafer of impregnated Cu, judge the state of oxidation of Cu.By the Cu peak of XPS (X-ray photoelectonspectroscopy) comparative observation from CuO, the growth rate of research Cu oxide-film.

Wherein, the compound below fluorine compounds that use in the soup of embodiment and comparative example and Cu surface protectant 1～3 use.

Fluorine compounds: NH ₄F

Cu surface protectant 1: indazole (production of ACROS ORGANICS society)

Cu surface protectant 2:2-mercaptobenzothiazoler (production of ACROS ORGANICS society)

Cu surface protectant 3:2,4,6-Triaminopyrimidine (production of ACROS ORGANICS society)

In table 2～12, represent embodiment, in table 12～15, represent comparative example.The judgment standard of expression result of the test in table 1.

Embodiment 1～27

The soup of embodiment 1～27 is according to the composition and the preparation of cooperation ratio of record in the table 2.PH is adjusted to about 6.5.The result of the soup test of embodiment 1～27 is used in expression in table 3.

Embodiment 28～41

The soup of embodiment 28～41 is according to the composition and the preparation of cooperation ratio of record in the table 4.The result of the soup test of embodiment 28～41 is used in expression in table 5.PH is adjusted to about 5.

Embodiment 42～53

The soup of embodiment 42～53 is according to the composition and the preparation of cooperation ratio of record in the table 6.The result of the soup test of embodiment 42～53 is used in expression in table 7.

Embodiment 54～86

The soup of embodiment 54～86 is according to the composition and the preparation of cooperation ratio of record in the table 8.The result of the soup test of embodiment 54～86 is used in expression in table 9.

Embodiment 87～94

The soup of embodiment 87～94 is according to the composition and the preparation of cooperation ratio of record in the table 10.The result of the soup test of embodiment 87～94 is used in expression in table 11.

[table 10]

[table 11]

Have according to the use shown in table 2～11 test pattern wafer evaluation result as can be known, the residue of embodiment 1～94 is removed liquid does not only make pattern form change but also the Cu surface can not produce coarse and small be full of cracks yet, can prevent simultaneously the oxidation of Cu, residue is removed excellent performance.

According to the evaluation result of using the pattern-free wafer as can be known, the etching speed of Cu and Low-k film is little, the contact angle of Low-k film does not change yet, thus expression do not have Cu corrosion and Low-k film owing to residue is removed the damage that liquid causes.

In embodiment 1～7, use acetonate, levulinate to replace glyoxylate, also show same effect.Use the 5-aminolevulinic acid also to show same effect.As aldehydic acid salt and/or ketone acid salt, also show same effect when using dimethylamine salt, front three amine salt, hydroxylamine salt, ethanolamine salt etc.

In embodiment 8～14, use the 5-aminolevulinic acid to replace levulinate, also show same effect.

In embodiment 22～27, use glyoxylate, acetonate, 5-aminolevulinic acid to replace levulinate, also show same effect.As aldehydic acid salt and/or ketone acid salt, also show same effect when using dimethylamine salt, front three amine salt, hydroxylamine salt etc.In addition, as neutral organic compound, use triethylene glycol, tetraethylene glycol, diethylene glycol monoethyl ether, diglycol monotertiary n-butyl ether, tripropylene glycol monomethyl ether, propylene glycol monoethyl ether acetate also to show same effect.Also show same effect when using 5-nitro indazole replaced C u surface protectant 1 (indazole).

In embodiment 9, use indazole-3-carboxylic acid to replace indazole, also show same effect.

In embodiment 28～31, use levulic acid to replace pyruvic acid, also show same effect.Also show same effect when using the 5-amino-laevulic acid.

In embodiment 36～41, use pyruvic acid to replace levulic acid, also show same effect.Use 5-amino-laevulic acid or KG also to show same effect.In addition, as neutral organic compound, use triethylene glycol, tetraethylene glycol, diethylene glycol monoethyl ether, diglycol monotertiary n-butyl ether, tripropylene glycol monomethyl ether, propylene glycol monoethyl ether acetate also to show same effect.

In embodiment 37～40, use 5-nitro indazole replaced C u surface protectant 1 (indazole) also to show same effect.

In embodiment 28～31, embodiment 36～41, also show same effect when using citrate to replace malonate.Use diammonium hydrogen citrate salt, dihydrogen citrate ammonium salt also to show same effect.

In embodiment 32～35, use malonate, diammonium hydrogen citrate salt, dihydrogen citrate ammonium salt to replace citrate also to show same effect.As the multi-carboxylate, also show same effect when using dimethylamine salt, front three amine salt, triethylamine salt, trien salt etc.

Embodiment 42～53 uses malonic acid to replace trifluoroacetic acid, also shows same effect.

Embodiment 42～53 uses oxalic acid, citric acid to replace trifluoroacetic acid, also shows same effect.

Embodiment 42～53 uses citrate to replace malonate, also shows same effect.Use diammonium hydrogen citrate salt, dihydrogen citrate ammonium salt also to show same effect.

When embodiment 46～53 uses methylamine salt as the multi-carboxylate, also show same effect.Also show same effect when using ethylamine salt, butylamine salt, dimethylamine salt, diethyl amine salt, front three amine salt, triethylamine salt, trien salt etc.

When embodiment 49～52 uses 5-nitro indazole replaced C u surface protectant 1 (indazole), also show same effect.

In embodiment 77～81, when using ammonia, methylamine, butylamine, diethylamine, propane diamine, trien, Tetramethylammonium hydroxide, choline etc. to replace diethylamine, also show same effect.

Embodiment 82～86 uses citrate, diammonium hydrogen citrate salt, dihydrogen citrate ammonium salt to replace malonate, also shows same effect.As the multi-carboxylate, when using methylamine salt, ethylamine salt, propylamine salt, butylamine salt, dimethylamine salt, diethyl amine salt, front three amine salt, triethylamine salt, Tetramethylammonium hydroxide salt, choline salt, propane diamine salt, trien salt etc. to replace ammonium salt, also show same effect.

When using 3-hydroxy indazole, 3-chloro-1H-indazole, 5-Aminoindazole, 5-nitro indazole, 6-nitro indazole, indazole-3-carboxylic acid replaced C u surface protectant 1 (indazole), also show same effect.

When using 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-thiazoline-2-mercaptan replaced C u surface protectant 2 (2-mercaptobenzothiazoles), also show same effect.

Use aminopyridine, 2, during 4-di-amino-pyrimidine replaced C u surface protectant 3 (2,4, the 6-Triaminopyrimidine), also show same effect.

When the fluoride salt of use methylamine, ethamine, diethylamine, Tetramethylammonium hydroxide replaces the fluorine compounds (ammonium fluoride) of embodiment 1～94, also show same effect.

When increasing the concentration of each composition among the embodiment 1～94, its effect also increases, even concentration being reduced to a half, also can give full play to its effect.

Comparative example 1～13

The soup of comparative example 1～13 is according to the composition and the preparation of cooperation ratio of record in the table 12.The result of the soup test of comparative example 1～13 is used in expression in table 13.

[table 12]

[table 13]

Comparative example 14～25

The soup of comparative example 14～25 is according to the composition and the preparation of cooperation ratio of record in the table 14.The result of the soup test of comparative example 14～25 is used in expression in table 15.

[table 14]

[table 15]

The soup of comparative example 1～9 and comparative example 14～19 is to be equivalent to the soup that the detergent remover behind the disclosed cmp (CMP) is formed in the patent documentation 1 (TOHKEMY 2001-148385).In patent documentation 1, enumerated the example that in carboxylic acid aqueous solutions such as oxalic acid, adds BTA and indazole etc., prevents the Cu oxidation.This soup is used to remove particle that metal on the Cu substrate surface and grinding etc. use or metal ion etc.

According to above-mentioned evaluation result, the soup of comparative example 1～9 and comparative example 14～19 can not be removed liquid as the residue after the dry process with effect of the present invention and use.

Claims

1. a residue is removed liquid, and the residue that it is used to remove on the semiconductor substrate that is present in after dry ecthing and/or the ashing is characterized in that:

Contain the Cu surface protectant, can form the compound and the water of complex or chelate with Cu (copper), the pH that this residue is removed liquid is 4～9, wherein,

2. residue as claimed in claim 1 is removed liquid, it is characterized in that:

Compound shown in above-mentioned (1) is to be selected from indazole class, pyrazoles and 1,2, the compound of 4-triazole type,

Compound shown in above-mentioned (2) is the compound of selected from mercapto imidazoles, Qiu Ji oxazole class, thyroidan class, mercaptothiazoline class, mercaptobenzimidazole class, mercaptobenzoxazole class and mercaptobenzothiazoler class,

Compound shown in above-mentioned (3) is the compound that is selected from pyridines, miazines, pyridazine class, pyrazine class, quinolines or quinazoline ditosylate salt, quinoxaline and cinnolines class.

3. residue as claimed in claim 1 is removed liquid, it is characterized in that:

Compound shown in above-mentioned (1) is to be selected from indazole, 3-hydroxy indazole, 3-chloro-1H-indazole, 5-Aminoindazole, 5-nitro indazole, 6-Aminoindazole, 6-nitro indazole, 3-bromo-7-nitro indazole, 7-nitro indazole, indazole-3-carboxylic acid, 1-benzyl-1H-indazole-3-alcohol, pyrazoles, 3,5-dimethyl pyrazole and 1,2, the compound of 4-triazole

Compound shown in above-mentioned (2) is the compound that is selected from 2-mercaptobenzimidazole, 2-mercaptoimidazole, 2-Qiu Ji oxazole, 2-mercaptobenzoxazole, 2-thyroidan, 2-mercaptobenzothiazole and 2-thiazoline-2-mercaptan,

Compound shown in above-mentioned (3) is to be selected from picoline, aminopyridine, 2,4-di-amino-pyrimidine, 2,4, the compound of 6-Triaminopyrimidine, pyridazine, the amino pyrazine of 3--2-carboxylic acid and 4-aminoquinoline.

4. residue as claimed in claim 1 is removed liquid, it is characterized in that:

The compound more than 2 kinds in the described Cu surface protectant above-mentioned by being selected from (1)～(3) constitutes.

5. residue as claimed in claim 1 is removed liquid, it is characterized in that:

The content that described residue is removed the Cu surface protectant in the liquid is 0.1～4000ppm.

6. residue as claimed in claim 1 is removed liquid, it is characterized in that:

The content that described residue is removed the Cu surface protectant that is made of the compound shown in above-mentioned (1) in the liquid is 0.1～3000ppm; the content of the Cu surface protectant that is made of the compound shown in above-mentioned (2) is 0.1～5ppm, and the content of the Cu surface protectant that is made of the compound shown in above-mentioned (3) is 10～1000ppm.

7. residue as claimed in claim 1 is removed liquid, it is characterized in that:

The described compound that can form complex or chelate with Cu be ketone acid, ketone acid salt, aldehydic acid salt, multi-carboxylate, can with Cu form complex or chelate strong acid, having can be at the neutral organic solvent of the oxygen atom of coordination on the Cu and/or the monohydric alcohol more than the C4.

8. residue as claimed in claim 7 is removed liquid, it is characterized in that:

The described compound that can form complex or chelate with Cu is at least a kind that is selected from ketone acid, ketone acid salt and the aldehydic acid salt.

9. residue as claimed in claim 7 is removed liquid, it is characterized in that:

The described compound that can form complex or chelate with Cu is the strong acid and the multi-carboxylate that can form complex or chelate with Cu.

10. residue as claimed in claim 7 is removed liquid, it is characterized in that:

The described compound that can form complex or chelate with Cu is that have more than 2 can be at the neutral organic compound of the oxygen atom of coordination on the Cu and/or the monohydric alcohol more than the C4.

11. residue as claimed in claim 7 is removed liquid, it is characterized in that:

The described compound that can form complex or chelate with Cu is a perchlorate.

12. residue as claimed in claim 1 is removed liquid, it is characterized in that:

Also contain fluorine compounds.

13. residue as claimed in claim 1 is removed liquid, it is characterized in that:

Also contain surfactant.

14. the method for removing of a residue, the residue that it is used to remove on the semiconductor substrate that is present in after dry ecthing and/or the ashing is characterized in that:

Making semiconductor substrate after dry ecthing and/or the ashing remove liquid with the described residue of claim 1 contacts.

15. residue removal method as claimed in claim 14 is characterized in that:

Described semiconductor substrate have Cu as wiring material, have film having low dielectric constant (Low-k film) as interlayer dielectic.

16. the manufacture method of a semiconductor equipment is characterized in that, comprising:

(1) to have Cu as wiring material, have film having low dielectric constant (Low-k film) carries out dry ecthing and/or ashing as the semiconductor substrate of interlayer dielectic operation; With

(2) make the semiconductor substrate after handling by above-mentioned (1) remove the operation that liquid contacts with the described residue of claim 1.

17. the manufacture method of semiconductor equipment as claimed in claim 16 is characterized in that:

Comprise that also (3) will be heated to the operation more than 180 ℃ by the semiconductor substrate after above-mentioned (2) processing in inert gas or in the vacuum.